1380494 九、發明說明 【發明所屬之技術領域】 ▼ 此發明乃關於色素增感光電變換元件模組及其製造方 法，以及光電變換元件模組及其製造方法以及電子機器， 對於例如使用載持色素之半導體微粒子所成之色素增感半 導體層之色素增感太陽能電池模組及各種電子機器，適用 且最佳之構成。 【先前技術】 作爲能源而使用石碳或石油等之石化燃料的情況，因 其結果產生的二氧化碳，將招致地球的暖化。另外，對於 使用原子能的情況係伴隨有經由放射線的污染之危險性。 就談論環境問題的現在，依存於此等能源之情況係有許多 重大問題。 另一方面，將太陽光變換成電量之光電變換裝置的太 Φ 陽能電池’係將太陽光作爲能量源之故，對於地球環境的 影響極小，期待有更進一層的普及。 作爲太陽能電池之材質係有各式各樣，但市售多爲使 用矽之構成’而此等係大略區分爲使用單結晶或多結晶的 矽之結晶矽系太陽電池，和使用非晶質（非晶形）矽系太 陽能電池。以往，對於太陽能電池，係多採用單結晶或多 結晶的矽，即結晶矽。 但是’在結晶砂系太陽能電池中，顯示將光（太陽） 能變換爲電能之性能的光變換效率，比較於非晶形矽太陽 -5- 1380494 能電池雖高’但對於結晶成長需許多的能量和時間之故， 生產性會變低，在成本面上不利。 另外’非晶質矽系太陽能電池’係有較結晶矽系太陽 能電池光吸收性高’基板的選擇範圍廣，大面積化容易等 之特徵’但光變換效率乃較結晶矽系太陽能電池爲低。更 且’非晶質矽系太陽能電池’生產性較結晶矽系太陽能電 池爲高，但與結晶矽系太陽能電池同樣地，在製造時需要 真空處理，在設備面上的負擔仍舊相當大。。 另一方面’朝向太陽能電池之更低成本化，硏究許多 取代砂系材料而使用有機材料之太陽能電池。但，其太陽 能電池的光變換效率係1 %以下非常的低，而對於耐久性 亦有問題。 在如此作爲中，報告有使用經由色素加以增感之半導 體爲例子的廉價之太陽能電池（参照Nature，3 5 3，p.737-740，1991)。此太陽能電池乃將對於增感色素使用釕複 合物而作爲分光增感的氧化鈦多孔質薄膜，作爲光電極之 濕式太陽能電池，即電性化學光電池。其色素增感太陽能 電池的優點ϋ採—角0價ϋ化欽，可m Μ运秦的先 吸收遍佈至800nm爲止之寬廣可視光波長域者，和光電 變換的量子效率爲高，高能量變換效率者。另外，對於製 造無需真空處理之故，而無需大型的設備等。更且’其色 素增感太陽能電池係具有「透視」、「可撓性」、「鮮豔 j等，對於以往之矽系太陽能電池無構思之故，在世界上 成爲注目。 -6- 1380494 近年，開發色素增感太陽能電池模組的動作處於活躍 化。在其色素增感太陽能電池模組之中，特別是活躍地進 行作爲支撐基材，使用塑料基板之可撓性太陽能電池模組 的開發。但，在一般的色素增感太陽能電池模組之製造工 程，爲了形成使用於色素增感半導體層之多孔質半導體層 的燒成處理乃必要，但如上述，作爲支撐基材而使用塑料 基板之情況，由於塑料基板的耐熱溫度（玻璃轉移溫度） 之關係，只能將燒成實之加熱溫度提昇至150 °C程度者。 因此，所得到之多孔質半導體層的結晶性或粒子間的結合 狀態變差，並在如此狀態下，電子導電性爲低之故，使用 塑料基板之色素增感太陽能電池模組的發電效率係對於使 用玻璃基板者而言，下降一半以上乃爲現狀。 因此，作爲欲解決此發明之課題，係提供可以輕量且 薄形而構成而構成可撓性，並且可得到高發電效率之色素 增感太陽能電池模組等之色素增感光電變換元件模組及其 製造方法，以及使用上述之優越色素增感光電變換元件模 組之電子機器。 作爲欲解決此發明之課題，係對於更一般而言，提供 可以輕量且薄形而構成而構成可撓性，並且可得到高發電 效率之包含色素增感太陽能電池模組或矽系太陽能電池等 之各種太陽能電池模組等之光電變換元件模組及其製造方 法，以及使用上述之優越光電變換元件模組之電子機器。 【發明內容】 1380494 爲了解決上述課題，第1發明乃屬於 於支撐基材上，具有複數之色素增感光電變換元件之 色素增感光電變換元件模組，其特徵乃 作爲上述支撐基材而使用厚度爲〇.2mm以下之薄膜 玻璃基板，且於上述色素增感光電變換元件模組之至少一 方的面，黏接有具有上述薄膜玻璃基板大小以上尺寸之樹 脂系的保護薄膜者。 在其第1發明，經由作爲支撐基材而使用薄膜玻璃基 板者，在使用於色素增感半導體層之多孔質半導體層的形 成時，例如可以5 00 °C程度之高溫，進行燒成處理之故， 多孔質半導體層的結晶性或粒子的結合狀態乃變爲良好， 從可得到高電子傳導性之情況，可得到高發電效率。另外 ，厚度爲0.2mm以下之薄膜玻璃基板係與塑料基板同樣 地，可容易地彎曲，不只是可撓性，且爲輕量。薄膜玻璃 基板係厚度越小越容易彎曲，雖亦關連於輕量化，但厚度 過小時，機械強度乃變爲過低之故，從此等觀點，存在有 理想的厚度，具體而言，〇.〇1〜〇.2mm爲佳。其厚度爲 0.2mm以_下之薄膜适每基板係亦可經由福_據_麻磨薄化Μ厚 之玻璃基板者而製作，亦可從最初使用製作爲其厚度之薄 膜玻璃基板。其薄膜玻璃基板的材質係特別無加以限制， 可使用以往公知之各種者，從其中做適當的選擇。其薄膜 玻璃基板係因應必要，亦可經由強化玻璃化而增加機械強 度者。 另一方面，當厚度爲0.2mm以下時，薄的薄膜玻璃 -8 - 1380494 基板係於表面或端面，存在有微小的龜裂產生或傷等時， 有容易產生斷裂。即，薄膜玻璃基板之機械強度係依存於 其薄膜玻璃基板之表面或端面之平滑性也不爲過。因此， 爲了防止薄膜玻璃基板之斷裂，進而防止色素增感光電變 換元件模組的防止，於色素增感光電變換元件模組之至少 一方的面，期望爲兩面，黏接具有其薄膜玻璃基板大小以 上尺寸之樹脂系的保護薄膜。經由將色素增感光電變換元 件模組之至少一方的面之全面，經由其保護薄膜加以被覆 者，可謀求對於其色素增感光電變換元件模組的彎曲之機 械性強度之大幅提昇，可使薄膜玻璃基板的斷裂飛躍地減 少，進而可防止色素增感光電變換元件模組之破壞者。爲 了謀求對於彎曲之色素增感光電變換元件模組之機械性強 度之更一層提昇，經由其保護薄膜，被覆薄膜玻璃基板之 端面之至少一部分，最佳爲盡可能爲多的部份爲佳。因此 ，對於僅於色素增感光電變換元件模組之一方的面黏接保 護薄膜之情況，將其保護薄膜摺疊而被覆薄膜玻璃基板之 端面者爲佳，對於於色素增感光電變換元件模組之兩面黏 接保護薄膜之情況，將此等保護薄膜之間，在從薄膜玻璃 基板露出的部份加以接合，被覆薄膜玻璃基板之端面爲佳 。薄膜玻璃基板之端面的保護係對於其薄膜玻璃基板之外 週全體而言進行爲佳’薄膜玻璃基板乃多角形，對於彎曲 的邊乃1邊以上決定之情況，作爲至少呈被覆其1邊以上 的端面者爲佳。作爲黏接於色素增感光電變換元件模組之 光入射側的面之保護薄膜及黏接劑，係使用透明的構成。 -9- 1380494 在其色素增感光電變換元件模組’典型而言’於薄膜 玻璃基板上之複數的範圍，各具有透明導電層’於其透明 導電層上，依序層積色素增感半導體層’多孔質絕緣層及 對極，構成色素增感光電變換元件’於色素增感光電變換 元件模組之色素增感光電變換元件側的面’黏接保護薄膜 ，經由其保護薄膜而被覆色素增感光電變換元件。對於相 互地電性串連連接薄膜玻璃基板上之複數色素增感光電變 換元件之情況，在相互鄰接之2個之色素增感光電變換元 件之間的部份，相互電性連接1個之色素增感光電變換元 件的透明導電層，和另1個之色素增感光電變換元件的對 極。對於色素增感半導體層及多孔質絕緣層，典型而言， 加上於色素增感半導體層及多孔質絕緣層，對於對極亦浸 含有電解質。形成於薄膜玻璃基板之複數的範圍之透明導 電層係亦可在層積色素增感半導體層、多孔質絕緣層及對 極之前，作爲圖案化，亦可在層積色素增感半導體層、多 孔質絕緣層及對極之後，作爲圖案化。其圖案化係可經由 以往公知之各種蝕刻法，雷射切割，物理性硏磨加工等而 進行者。 形成於薄膜玻璃基板之透明導電層的表面阻抗（薄片 阻抗）係越低爲佳。具體而言，透明導電層之表面阻抗乃 5 00 Ω/ □以下爲佳，而100Ω/ □爲更佳。作爲其透明 導電層之材料乃可使用公知的材料，具體而言可列舉銦-錫複合氧化物（ITO)、摻雜氟之Sn02(FT0)、摻雜銻 之 Sn02 ( ΑΤΟ) 、Sn02、ΖηΟ、銦-鋅複合氧化物（ΙΖΟ ) -10- 1380494 等，但並不限定於此等，另外，而亦可將此等組合2種以 上而使用。另外，以降低形成透明導電層於其薄膜玻璃基 » 板之透明導電性基板的表面阻抗’使集電效率提昇之目的 ，於其薄膜玻璃基板上，亦可另外設置導電性高之金屬等 或碳等之導電材料所成之配線。對於使用於其配線之導電 材料雖未特別加以限制，以耐蝕性、耐氧化性高，導電材 料本身之漏電流爲低者爲佳。 • 色素增感半導體層係典型而言，載持色素之半導體微 粒子所成之多孔質半導體層。做爲半導體微粒子之材料， 除了矽爲代表之元素半導體材料之外，可使用各種之化合 物半導體，具有鈣鈦礦構造之化合物等。此等之半導體材 料乃在光激發下，傳導帶電子呈載體，產生陽極電流之η 型半導體者爲佳。此等半導體係當具體例示時，爲Ti02 ' ZnO、W03 ' Nb205 ' TiSr03、Sn02 等，在此等之中， 銳鈦礦型之Ti〇2乃特別理想。半導體的種類係並無限定 ® 於此等，另外，亦可將此等作爲混合2種以上地加以使用 。又，半導體微粒子乃依需要可呈粒狀 '管狀、棒狀等之 各種形態。 對於半導體微粒小之粒徑，雖未特別加以限制，一次 粒子之平均粒徑爲1〜200nm爲佳，尤以5〜1 OOnm更佳 。另外，亦可於其平均粒徑的半導體微粒子，混合較其平 均粒徑爲大之平均粒徑的半導體微粒子，經由平均粒徑大 之半導體微粒子，使入射光散亂，而可提升量子產率。此 情況，另外混合之半導體微粒子之平均粒徑爲20〜5 OOnm -11 - 1380494 爲佳。 半導體微粒子所成之半導體層之製膜方法雖未特別加 以限定，考量物性、方便性、製造成本等之時，以濕式製 膜者爲佳，以調製將半導體微粒子之粉末或溶膠均勻分散 於水或有機溶媒等之溶劑，塗佈於透明導電性基板上之方 法爲佳。塗佈係對於其方法無特別加以限制，可依照公知 的方法加以進行，例如可使用浸漬法、噴霧法、環棒式塗 佈法、旋塗法、輥塗佈法、刮刀塗佈、照相凹版塗佈法等 ’又做爲濕式印刷方法，例如可經由凸版、膠版、照相凹 版、凹版印刷法、橡膠版及網版印刷法等各種方法而進行 。作爲半導體爲例子的材料而使用結晶氧化鈦之情況，其 結晶型係銳鈦礦型乃從光觸媒活性的點爲佳。銳鈦礦型氧 化鈦乃可爲市售之粉末狀、溶膠狀或淤漿狀，或經由加水 分解氧化鈦醇鹽等之分知方法，形成特定之粒徑者亦可。 使用市售之粉末時，解除粒子之二次凝聚者爲佳，於塗佈 液之調製時，使用乳鉢或球磨機或超音波分散裝置等，進 行粒子之粉碎爲佳。此時，爲防止解除二次凝聚之粒子的 再度凝聚，可添加乙醯丙酮、鹽酸、ϋ酸、_界面洁性劑及 螯合劑等。又，爲增加之黏性，可添加多聚氧化乙烯或聚 乙烯醇等之高分子，纖維素系之增黏劑等之各種增黏劑等 〇 由半導體微粒子所成之半導體層，換言之，半導體微 粒子層係呈可吸付多的增感色素地，表面積爲大之構成者 爲佳。爲此，將半導體微粒子層塗設於支撐體上之狀態的 -12- 1380494 表面積乃對於投影面積而言，爲ίο倍以上者爲佳， 爲1 00倍以上者更佳。此上限雖無特別加以限制，但 爲1 000倍之程度。半導體微粒子係一般而言，其厚 增加，對每單位投影面積之載持色素量越增加之故， 擷取率則變高，但所注入之電子的擴散距離增加之故 由電荷再結合之損失亦變大。隨之，對於半導體微粒 雖存在較佳之厚，但其厚度一般而言，爲〇_1〜100// 更佳爲1〜50//m，尤其更佳爲3〜30//m。半導體微 層係在塗不虞支撐體之後，使粒子之間做電子性接觸 使膜強度提昇或提昇與基板的密著性，進行燒成者爲 燒成溫度之範圍雖未特別加以限制，溫度過高之時， 之電阻會變高，更且，有熔融之情形，通常以4(TC， °C爲佳，更佳爲40°C〜65 0 °C。又，燒成時間雖亦無 限制，通常爲1 〇分〜1 〇小時程度。燒成後，在增加 體微粒子層之表面積，爲提高半導體微粒子間之頸縮 目的下，例如可進行使用四氯化鈦水溶液之化學電鍍 使用三氯化钛水溶液之頸縮處理，或直徑1 Onm以下 導體氧化鈦超微粒子溶膠的浸漬處理。 例如做爲載持於半導體層之色素，如爲顯示增感 之構成，並無特別加以限制，但可列舉若丹明B、玫 、曙红、红霉素等之氧雜蔥系色素、部花青、隱花青 青系色素、酚藏花红、卡布利藍、硫代西涅、亞甲基 之鹽基性染料、葉綠素、鋅卟啉、鎂卟啉等之卟啉系 物，作爲其他之構成，可舉出偶氮色素、酞花青系化 更且 通常 度越 光的 ，經 子層 m， 粒子 ，爲 佳。 基板 -700 特別 半導 之下 ，或 之半 作用 瑰紅 等花 藍等 化合 合物 -13- 1380494 、香豆素系化合物、Ru聯吡啶錯化合物、Ru三聯吡啶錯 化合物、蒽醌系色素、多環醌系色素、方酸鑰等。此等之 中，尤以Ru聯吡啶錯化合物係量子產率爲高，特別理想 。但，增感色素係並無限定於此等，另外，亦可將此等增 感色素作爲混合2種以上地加以使用》 對於係吸付於色素之半導體層之方法，雖未特別加以 限制，亦可將上述之增感色素以例如溶解於醇類、腈類、 硝基甲烷、鹵化碳化氫、醚類、二甲亞砸、醯胺類、N-甲 基吡咯烷酮、1,3-二甲基咪唑啉二酮、3-甲基噁唑烷酮、 酯類、碳酸酯類、酮類、碳化氫、及水等溶劑，於此浸漬 半導體層，或將色素溶液塗佈於半導體層上。另外，對於 使用酸性度高之色素情況，以減少色素間之會合，亦可添 加脫氧膽酸等。 在吸付增感色素之後，以促進過度吸附之增感色素的 除去爲目的，亦可使用胺類，處理半導體電極之表面。做 爲胺類之例，可列舉毗啶、4-特·丁基吡啶、聚乙烯吡咯 烷酮等，此等乃液體之情況係亦可直接使用，亦可溶解於 有機溶劑而使用。。 · 多孔質絕緣層之材料係如爲未具導電性之材料，並無 特別加以限制，但特別使用包含選自Zr、A卜Ti、Si、Zn 、…及Nb所成的群之中至少1種以上的元素之氧化物， 其中，使用之氧化物，其中，使用氧化銷，氧化鋁，二氧 化鈦，二氧化矽等者爲佳，典型來說矽使用其氧化物之微 粒子。其多孔質絕緣層之空孔率乃1 0%以上者爲佳。對於 -14- 1380494 空孔率的上限雖無限制，徉其多孔質絕緣層之物理性的強 度之觀點，通常乃10〜80%程度爲佳。當空孔率乃10%以 下時，對於電解質之擴散帶來影響，顯著地使色素增感光 電變換元件模組之特性下降。另外，其多孔質絕緣層的細 孔徑乃1〜l〇〇〇nm爲佳。當細孔徑乃未達lnm時，對於 電解質之擴散或色素帶來影響，使色素增感光電變換元件 模組之特性下降。更且，細孔徑乃較lOOOnm爲大時，於 多孔質絕緣層中侵入有對極之觸媒粒子之故，有產生短路 之虞。對於其多孔質絕緣層之製造方法雖無限制，但上述 氧化物粒子的燒結體者爲佳。 對於對極的材料並無特別加以限制，具有觸媒活性之 物質本身乃如具有導電性，可直接使用，對於觸媒本身未 具有導電性之情況，亦可組合導電性物質與具有觸媒活性 之物質而使用者。對極係具體而言，例如含有選自Pt、 Ru、Ir及C所成的群之至少一種以上的元素者爲佳，其 中，包含Pt或C者爲佳，特別包含C之材料的炭黒乃爲 廉價之故而爲理想。 對極係於金屬或合金所成的箔之多孔質絕緣層側的單 面，具有觸媒層者，或經由具有催化活性之材料所成的箔 而構成亦可。經由如此作爲，可薄化構成對極之故，可進 行色素增感光電變換元件模組的薄型化及輕量化。另外， 構成對極之金屬或合金所成的箔之材料及具有觸媒層之材 料係選擇幅度，無在對極的材料面之限制。更且，色素增 感半導體層與對極係由多孔質絕緣層所間隔之故，可防止 -15- 1380494 色素增感半導體層的色素乃附著對極者’不會產生特性的 劣化。構成其對極之金屬或合金所成的箔係使用含有選自 Ti、Ni、Cr、Fe、Nb、Ta、W、Co及Zr所成的群之至少 1種類以上元素之金屬或合金所成的箔者爲佳。設置於金 屬或合金所成的箔之多孔質絕緣層側的單面之觸媒層，或 具有觸媒層之材料乃包含選自Pt、Ru、Ir及C所成的群 之至少1種以上元素者爲佳。從色素增感光電變換元件模 組的薄型化觀點，對極的厚度，即金屬或合金所成的箔與 觸媒層的厚度之合計或具有觸媒層之材料所成的箔之厚度 乃0.1mm以下者爲佳。對於於金屬或合金所成的箔之上 方載持觸媒層，係可使用濕式塗佈含有觸媒或觸媒之前驅 體之溶液的方法，或濺鍍法，真空蒸鍍法，化學氣相成長 (CVD )等之乾式法等》此情況，對極與透明導電層係亦 可相互直接接合，亦可藉由導電材料加以接合。後者之情 況，具體而言，將對極與透明導電層，例如經由導電性黏 接劑或融點爲300°C以下之低融點金屬或合金相互加以接 合。作爲導電性黏接劑’可使用市售的銀，碳，鎳，銅膠 漿等之外’亦可使用異向性導電性黏接劑或薄膜狀之構成 。另外’亦可使用可接合於透明導電層之In或In-Sn系 焊料等各種低融點金屬或合金。另外，對於對極與透明導 電層之接合部與電解質直接接觸之情況，亦可作爲由樹脂 等保護接合部而防止與電解質之接觸。 保護薄膜的材質係如爲樹脂系，並無特別加以限定， 但最佳係使用具有高氣體阻障性之材料，具體而言，例如 -16- 1380494 使用氧透過度爲l〇〇(cc/m2/day/atm)以下、水蒸氣 透過度乃1〇〇 ( g/ m2/ day )以下者。作爲其保護薄膜， 係例如使用由食品外裝薄膜等所代表之氣體阻障性薄膜， 最佳係使用層積選自鋁，二氧化矽及氧化鋁所成的群之至 少1種類以上之氣體阻障材料之氣體阻障性薄膜等。其保 護薄膜係最佳爲使用適當之黏接劑，在減壓下或不活性氣 體環境中加以密封》經由將如此的保護薄膜，設置於色素 增感光電變換元件模組之色素增感光電變換元件側的面或 薄膜玻璃基板之背面側之時，因可防止從外部浸透氧等之 氣體或水蒸氣等於色素增感光電變換元件模組的內部，故 可抑制光電變換效率等之特性的劣化，進而可謀求色素增 感光電變換元件模組之耐久性的提升。使用於保護薄膜的 黏接之黏接層的材質係並無特別加以限定，但使用氣體阻 障性高，對於化學性不活性，電性絕緣性之材料爲佳，具 體而言，可使用樹脂，玻璃料等，更具體而言，例如可使 用環氧樹脂，胺甲酸乙酯樹脂，聚矽氧樹脂，丙烯酸樹脂 等之各種紫外線（UV )硬化型樹脂，各種熱硬化型樹脂 ，熱熔樹脂’低熔點玻璃料等。其黏接層係與保護薄膜作 爲一體化者爲佳，但並不限定於此。 電解質係除了碘（12)與金屬碘化物或有機碘化物之 組合’溴（Br2 )與金屬溴化物或有機溴化物之組合以外 ’可使用亞鐵化氰酸鹽/鐵氰酸鹽或二茂鐵/鐵錫離子等 之金屬複合物，聚硫化鈉，烷基硫醇基/烷基二硫化物等 之硫化合物’紫羅城色素，對苯二酚/醌等。作爲金屬化 -17- 1380494 合物之陽離子乃Li、Na、K、Mg、Ca、Cs等，作爲有機化 合物之陽離子乃四烷基錢基類，啦啶類，咪唑類等之4級銨 化合物爲佳，但並不限於此等，另外亦可將此等做2種以 上混合使用。其中，組合12與Lil、Nal或咪唑碘鹽等之 4級銨化合物之電解質爲佳。電解質鹽之濃度乃對於溶媒 而言，較佳爲〇·〇5Μ〜10M、更佳爲0.2M〜3M。12或Br2 之濃度，較佳爲0.0005Μ〜1Μ、更佳爲 0.001Μ〜0.3Μ。 另外，提升開放電壓爲目的下，可加上4-特-丁基吡啶所 代表之氨系化合物所成之添加劑。 做爲構成電解液之溶媒，雖可列舉水、醇類、醚類、 酯類、碳酸酯類、內酯類、羧酸酯、磷酸三酯類、雜環化 合物類、腈類、酮類、胺類、硝基甲烷、鹵素化碳化氫、 二甲亞楓、環丁楓、Ν-甲基吡咯烷酮、1,3-二甲基咪唑啉 二酮、3 -甲基噁唑烷酮、碳化氫等，但非限定於此，亦可 將此等做混合2種以上加以使用。更且，做爲溶媒，亦可 使用四烷基系、吡啶系、咪唑系第4級銨鹽之離子性液體 減少色素增感型光電變換_元件之—漏—液、—《齒—液乏瘅 發之目的下，於上述電解質構成物，溶解凝膠劑、聚合物 或交聯單體等之外，亦可使無機陶瓷粒子分散，做爲凝膠 狀電解質加以使用。凝膠矩陣與電解質組成物的比率乃如 電解質組成物爲多時，離子導電率變高，但機械性強度下 降，相反地，如電解質組成物過少時，機械性強度爲大， 但離子導電率下降之故，電解質組成物係期望爲凝膠狀電 -18- 1380494 解質之50〜99 wt %，而更佳爲80〜97wt %。另外，由將上 述電解質與可塑劑溶解於聚合物，揮發可塑劑加以除去， 亦可實現全固體型之色素光增感光電變換元件模組。 色素光增感光電變換元件模組的製造方法並無特別加 以限定，但考慮各層的厚度，生產性，圖案精確度等時， 對於在吸付色素前之半導體層，多孔質絕緣層，對極及接 觸層，更且對極乃具有觸媒層者之情況，其觸媒層係全部 經由網版印刷或噴墨塗佈等之濕式塗佈法而形成者爲佳， 特別是經由網版印刷而形成者爲佳。在吸付色素前之半導 體層及多孔質絕緣層係經由含有構成各個層之粒子的塗漿 的塗佈，燒成而形成者爲佳。各自的空孔率係經由塗漿的 黏合成分與粒子的比而加以決定。對極亦同樣地經由塗漿 的塗佈，燒成而形成者爲佳，但對於對極之色素附著乃對 於特性有影響之情況，在形成至半導體層及多孔質絕緣層 的階段，於半導體層吸付色素，之後於多孔質絕緣層上形 成對極亦可。經由於金屬或合金所成的箔之多孔質絕緣層 側的單面具有觸媒層者，構成對極之情況，係將其金屬或 合金所成的箱上之觸媒層’朝向多孔質絕緣層’與旁邊的 色素增感光電變換元件之透明導電層接合。爲使電解質含 於各色素增感光電變換元件之色素增感半導體層或多孔質 絕緣層等之電解質的塡充’例如可使用酚配器或印刷’噴 墨等之方法而進行。但’在串連地連接複數之色素增感光 電變換元件之色素增感光電變換元件模組中’經由流出有' 電解質者而在色素增感光電變換元件間產生短路之故’添 -19- 1380494 加浸含於各色素增感光電變換元件之色素增感半導體層或 多孔質絕緣層等之量以上的量之電解質者爲佳。 色素增感光電變換元件模組乃對應於該用途，可以各 種形狀加以製作，該形狀則未特別加以限定。色素增感光 電變換元件模組乃對於最典型而言，作爲色素增感太陽能 電池模組而加以構成。但，色素增感光電變換元件模組乃 除色素增感太陽能電池模組之外，例如亦可爲色素增感光 感測器。 第2發明， 屬於於支撐基材上，具有複數之色素增感光電變換元 件之色素增感光電變換元件模組之製造方法，其特徵乃具 有： 作爲上述支撐基材而使用厚度爲〇.2mm以下之薄膜 玻璃基板，於其薄膜玻璃基板上形成上述複數之色素增感 光電變換元件，形成色素增感光電變換元件模組的工程， 和於上述色素增感光電變換元件模組之至少一方的面 ，黏接有具有上述薄膜玻璃基板大小以上尺寸之樹脂系的 保護薄膜的工程者。 在其色素增感光電變換元件模組之製造方法，典型而 言，於透明導電層上，依序層積色素增感半導體層，多孔 質絕緣層及對極而形成色素增感光電變換元件時，在相互 鄰接之2個之色素增感光電變換元件之間的部份，相互電 性連接1個之色素增感光電變換元件的透明導電層，和另 1個之色素增感光電變換元件的對極。 -20- l38〇494 在第2發明，上述以外的情況係在不違反其性質，關 連於第1發明而說明者乃成立。 第3發明， 針對使用色素增感光電變換元件模組之電子機器， 上述色素增感光電變換元件模組乃屬於 於支撐基材上，具有複數之色素增感光電變換元件之 色素增感光電變換元件模組，其特徵乃 作爲上述支撐基材而使用厚度爲0.2mm以下之薄膜 玻璃基板，且於上述色素增感光電變換元件模組之至少一 方的面，黏接有具有上述薄膜玻璃基板大小以上尺寸之樹 脂系的保護薄膜者。 電子機器係基本尙上可爲任何構成，包含攜帶型之構 成和放置型之構成雙方，但舉出具體例時，有行動電話， 移動機器，機器人，個人電腦，車載機器，各種家庭電器 製品等。此情況，色素增感光電變換元件模組係例如作爲 此等電子機器之電源所使用之色素增感太陽能電池模組。 在第3發明，上述以外的情況係在不違反其性質，關 連於第1發明而說明者乃成立。 第4發明， 一種於支撐基材上，具有複數之光電變換元件之光電 變換元件模組，其特徵乃 作爲上述支撐基材而使用厚度爲0.2mm以下之薄膜 玻璃基板，且於上述色素增感光電變換元件模組之至少一 方的面，黏接有具有上述薄膜玻璃基板大小以上尺寸之樹 -21 - 1380494 脂系的保護薄膜者。 第5發明， 一種於支撐基材上，具有複數之光電變換元件之光電 變換元件模組之製造方法，其特徵乃具有： 作爲上述支撐基材而使用厚度爲0.2mm以下之薄膜 玻璃基板，於其薄膜玻璃基板上形成上述複數之光電變換 元件，形成上述光電變換元件模組的工程， 和於上述光電變換元件模組之至少一方的面，黏接有 具有上述薄膜玻璃基板大小以上尺寸之樹脂系的保護薄膜 的工程者。 第6發明， 針對使用光電變換元件模組之電子機器， 上述光電變換元件模組乃屬於 於支撐基材上，具有複數之光電變換元件之光電變換 元件模組，其特徵乃作爲上述支撐基材而使用厚度爲 0.2mm以下之薄膜玻璃基板，且於上述光電變換元件模組 之至少一方的面，黏接有具有上述薄膜玻璃基板大小以上 尺寸之樹脂系的保護薄膜者。 在第4〜第6發明，對於光電變換元件，不只色素增 感太陽能電池等之色素增感光電變換元件，亦包含有矽系 太陽能電池等之以往公知的光電變換元件。 在第4〜第6發明，上述以外的情況係在不違反其性 質，關連於第]〜第3發明而說明者乃成立* 在如以上所構成之此發明，作爲支撐基材所使用之厚 -22- 1380494 度乃0.2mra以下薄的薄膜玻璃基板乃可撓性，且輕量。 另外，經由黏接於色素增感光電變換元件模組或光電變換 元件模組之至少一方的面，具有薄膜玻璃基板大小以上尺 寸之樹脂系的保護薄膜，可謀求色素增感光電變換元件模 組或光電變換元件模組之機械性強度的提升。加上，其薄 膜玻璃基板係亦可承受在500°C程度之溫度的加熱。因此 ，在色素增感光電變換元件中，在使用於色素增感半導體 層之多孔質半導體層的形成時，例如可以5 0 0 °C程度之高 溫，進行燒成處理之故，多孔質半導體層的結晶性或粒子 的結合狀態乃變爲良好，從可得到高電子傳導性之情況， 進而可得到高發電效率。另外，在矽系光電變換元件中， 可將矽膜的成膜或熱處理等之處理，在至50(TC程度之高 溫度進行之故，可得到良質的矽膜，進而可得到高發電效 率。 如根據此發明，可實現以輕量且薄型構成爲可撓性， 且可得到高發電效率之色素增感光電變換元件模組或光電 變換元件模組。並且，可使用其優越之色素增感光電變換 元件模組或光電變換元件模組之而實現高性能之電子機器 〇 【實施方式】 以下，對於本發明之實施形態，參照圖面同時加以說 明。然而，在以下的實施型態’對於同一或對應之部分則 附上同〜·符號。 -23- 1380494 圖1〜圖3乃顯示根據本發明之第1實施形態之色素 增感光電變換元件模組。在此，圖1乃其色素增感光電變 換元件模組之剖面圖，圖2乃其色素增感型光電變換元件 模組之要部剖面圖，圖3乃其色素增感光電變換元件模組 之平面圖。圖1乃相當於沿著圖3之X-X線之剖面圖， 圖2係相當於沿著圖3之X-X線之一部分擴大剖面圖。 如圖1〜圖3所示，在其色素增感型光電變換元件模 組，於絕緣性，且透明之薄膜玻璃基板1上，複數，相互 平行地設置條紋狀之透明導電層。其薄膜玻璃基板1之厚 度係作爲〇.2mm以下，最佳爲0.01〜0.2mm。對於各透明 導電層2上，依序層積各延伸存在於與透明導電層2同一 方向之條紋狀的色素增感半導體層3，多孔質半導體層4 及對極5，構成色素增感光電變換元件。至少於色素增感 半導體層3及多孔質絕緣層4之全體’典型而言’於此等 色素增感半導體層3及多孔質絕緣層4與對極5之全體’ 浸含有電解質。此情況，色素增感半導體層3的寬度乃較 透明導電層2爲小，鄰接於透明導電層2之長度方向的一 邊之部分則露出。多孔質絕緣層4之寬度乃S色素增感半 導體層3的寬度爲大，呈被覆色素增感半導體層3之全體 地加以設置。多孔質絕緣層4之—端係沿著色素增感半導 體層3之一方的側面而延伸存在’與薄膜玻璃基板1接合 ，另—端係沿著色素增感半導體層3之另一方的側面而延 伸存在，與透明導電層2接合。另外，1個之色素增感光 電變換元件的對極5之一端係與鄰接之色素增感光電變換 -24- 1380494 元件之透明導電層2加以接合。由此’相互電性串連地連 接複數之色素增感光電變換元件。在圖1及圖3 ’圖示有 串連地連接8個色素增感光電變換元件之情況’但串連地 連接之色素增感光電變換元件的數量係因應於必要而加以 選擇，當然並不限定於8個。對於形成有此等之串聯連接 之複數色素增感光電變換元件之一端的色素增感光電變換 元件之透明導電層2，係連接有取出電極6，對於鄰接於 形成有另一端之色素增感光電變換元件之透明導電層2加 以形成，連接其色素增感光電變換元件之對極5的一端之 透明導電層2，係連接取出電極7。於各色素增感光電變 換元件之間的對極5與多孔質絕緣層4之間的部份及對極 5的全面，設置黏接層8，於其黏接層8的全面，黏接較 薄膜玻璃基板1尺寸爲大之樹脂系的保護薄膜9。另一方 面，於薄膜玻璃基板1背面之全體，設置黏接層10，於 其黏接層10的全面，黏接較薄膜玻璃基板1尺寸爲大之 樹脂系的保護薄膜11。並且，保護薄膜9與保護薄膜11 係在從薄膜玻璃基板1露出的部份相互加以接合，由此， 薄膜玻璃基板1的端面，亦經由保護薄膜9加以被覆。作 爲黏接於光入射面側之保護薄膜Π及保護薄膜9，係使 用透明之構成，但作爲保護薄膜9及黏接層8係亦可使用 透明之構成，並非如此構成亦可。於圖4顯示擴大多孔質 絕緣層4，對極5及黏接層8之一部分（以圖3之一點虛 線圍住的部份）之平面圖。 做爲色素增感半導體層3，使用於半導體微粒子層或 -25- 1380494 多孔質半導體層，載持色素者。對於保護薄膜9，11的至 少一方係最佳爲由氣體阻障材料所成之樹脂系的箔膜，例 如使用氧透過度爲100(cc/m2/day/atm)以下、水蒸 氣透過度乃l〇〇(g/m2/day)以下者。另外，作爲光入 射側之保護薄膜1 1，最佳係爲了控制經由反射的入射光 之光量損失，使用無反射（AR)薄膜。 薄膜玻璃基板1，透明導電層2，色素增感半導體層 3，多孔質絕緣層4，對極5及黏接層8，10係從既已舉 出的構成中，可使用因應必要所選擇者。 接著，對於其色素增感光電變換元件模組之製造方法 加以說明。 首先，如圖5的A所示，準備薄膜玻璃基板1，於其 薄膜玻璃基板1的全面，形成透明導電層2之後，將其透 明導電層2，經由蝕刻而圖案化爲條紋狀。在此，作爲薄 膜玻璃基板1，從最初厚度爲〇.2mm以下之構成亦可，亦 可使用厚度較〇.2mm爲大之構成》對於後者之情況，之 後將薄膜玻璃基板1，經由硏磨等而加以薄化，作爲 0.2mm_以下的厚度。备著，於各透明導電層—2上，將H 有半導體微粒子之塗漿，塗佈爲特定之間隔。接著，將薄 膜玻璃基板〗加熱爲特定溫度，燒結半導體微粒子’形成 半導體微粒子燒結體所成之多孔質半導體層。 接著，於全面形成多孔質絕緣層4之後，將其多孔質 絕緣層4，經由蝕刻而圖案化爲條紋狀。接著，於其多孔 質絕緣層4之全面形成對極5，將其對極5的一端’與各 -26- 1380494 透明導電層2接合。 接著，將半導體微粒子燒結體所成之多孔質半導體層 ，形成有多孔質絕緣層4及對極5之薄膜玻璃基板1，作 爲浸漬於色素溶液等，於構成多孔質半導體層之半導體微 粒子，載持增感用之色素，形成色素增感半導體層3。 接著，對於對極5側之表面，塗佈電解質，將其電解 質，至少浸含於色素增感半導體層3及多孔質絕緣層4之 φ 全體，典型而言，浸含於此等色素增感半導體層3及多孔 質絕緣層4與對極5之全體。 接著，於鄰接於形成有一端之色素增感光電變換元件 之透明導電層2及形成有另一端之色素增感光電變換元件 之透明導電層2所形成之透明導電層2，接合各取出電極 6，7 〇 接著，如圖5的B所示，於對極5側之表面，藉由黏 接層8而黏接保護薄膜9。 # 接著，對於作爲薄膜玻璃基板1而使用厚度較〇.2mm 爲大之構成情況，將薄膜玻璃基板1，經由硏磨等而加以 薄化，將厚度作爲〇.2mm以下。 之後，於薄膜玻璃基板1的背面，藉由黏接層1〇而 黏接保護薄膜11，在從薄膜玻璃基板1露出的部份，接 合其保護薄膜11與保護薄膜9，將薄膜玻璃基板1的端 面，經由保護薄膜9加以被覆。如以上作爲，製造圖1〜 圖3所示之色素增感光電變換元件模組。 接著，對於其色素增感光電變換元件模組之動作加以 -27- 1380494 說明。 從薄膜玻璃基板1側透過其薄膜玻璃基板1而入射的 光，係激發色素增感半導體層3的色素而產生電子。其電 子乃迅速從色素引渡至色素增感半導體層3之半導體微粒 子。另一方面，失去電子的色素乃從浸含於色素增感半導 體層3及多孔質絕緣層4的全體之電解質的離子，接受電 子，引渡電子之分子乃再次在對極5的表面，接受電子》 經由其一連串的反應，於與色素增感半導體層3電性連接 之透明導電層2與對極5之間，產生起電力。由此進行光 電變換。此情況，於連接於串聯連接之複數色素增感光電 變換元件之一端的色素增感光電變換元件之透明導電層2 的取出電極6與連接於另一端的色素增感光電變換元件之 透明導電層2的取出電極7之間，產生各色素增感光電變 換元件之起電力的合計起電力。 如根據其第1實施型態，因作爲支撐基材，使用厚度 爲0.2 mm以下，最佳爲〇.〇1〜0.2mm之薄膜玻璃基板1， 色素增感光電變換元件側之全面及薄膜玻璃基板1的端面 乃經由《護薄以被覆；薄膜^ 之W®荃 體乃經由保護薄膜11加以被覆之故，可將色素增感光電 變換元件模組，以輕量且薄型而構成爲可撓性，亦可充分 地確保色素增感光電變換元件模組之機械性強度者。另外 ’因作爲支撐基材而使用薄膜玻璃基板1，故可將使用於 色素增感半導體層3之多孔質半導體層的形成時之燒成處 理，由500°C程度之溫度進行，經由此可將多孔質半導體 -28- 1380494 層之結晶性或粒子的結合狀態作爲良好，進而可將 導性作爲良好者。因此，可提昇色素增感光電變換 組之發電效率。更且，經由作爲保護薄膜9，11而 氣體阻障材料所成之薄膜者，可防止從外部，氧等 或水蒸氣等浸透於模組內部，進而可防止光電變換 之特性的劣化。因此’可實現可維持長期優越特性 性高的色素增感光電變換元件模組。另外，色素增 體層3與對極5係由多孔質絕緣層4所間隔之故， 色素增感半導體層3的色素附著對極5者，從不會 性的劣化，可實現具有與Z型構造之色素增感太陽 模組同等之發電性能的色素增感光電變換元件模組 對於其色素增感光電變換元件模組之實施例加 實施例1 準備於尺寸爲60mmx46mm，厚度爲4mm之玻 上，形成有FTO膜之曰本板硝子製非晶形太陽能 FTO玻璃基板（薄片阻抗10Ω/ΕΙ)，將其FTO 由蝕刻加以圖案化，於之間呈形成〇.5mm寬度的 形成9條條紋狀的圖案。之後，依序使用丙酮，醇 洗淨液，超純水，進行超音波洗淨，使其充分乾燥 於除了其FTO玻璃基板上之9條FTO膜之中 的1條之8條的FTO膜上，將Solaronix製氧化鈦 以寬度5mm，長度40mm之條紋狀，8條（總面積 電子傳 元件模 使用由 之氣體 效率等 之耐久 感半導 可防止 產生特 能電池 〇 以說明 璃基板 電池用 膜，經 間隙地 ，鹼系 〇 的末端 塗漿’ 1 6cm2 -29 - 1380494 )、由網版印刷機加以塗佈》塗漿係從玻璃機板側，依序 使透明之Ti-Nanoxide TSP塗漿，層積厚度7//m、使含 有散亂粒子之Ti-Nanoxide DSP，層積厚度13；tzm，得到 合計20/im之厚度的多孔質Ti02膜。將其多孔質Ti02膜 ，以5 00 °C，30分鐘由電器爐加以燒成，放冷後，浸漬於 O.lmol/L之TiCl4水溶液中，以70°C進行30分鐘保持 ，充分地以純水及乙醇洗淨，乾燥後，再次以500 °C，30 分鐘由電器爐加以燒成。如此作爲，製作Ti02燒結體。 接著，將使用市售的Ti02粒子（粒徑200nm)，萜 品醇及乙基纖維素而調製之網版印刷用Ti02塗漿，以長 度41mm、寬度5.5mm、厚度l〇Am塗佈於上述Ti〇2燒 結體上。使其丁丨02塗漿乾燥，將作爲對極而使用市售之 碳黑與石墨粒子，萜品醇及乙基纖維素而調製之網版印刷 用Ti02塗獎，以長度40mm、寬度6mm、厚度30# m塗 佈於上述Ti02層上，在使其塗漿乾燥後，以450°C，30 分鐘由電器爐加以燒成。如此作爲而形成多孔質絕緣層及 多孔質的對極。 接著，於0.5mM順式雙（異氰硫基)-N，N-雙（2,2’-吡啶-4,4’-二羧酸）釕（II)二四丁基銨鹽（N719色素） 之tert·丁醇/乙腈混合溶劑（體積比1:1)，室溫下， 進行48小時浸漬，於Ti02燒結體，載持色素。將由如此 作爲載持色素之Ti02燒結體，乙腈加以洗淨，在暗處使 其乾燥。如此作爲，製作色素增感Ti02燒結體。 於r-丁内酯3g，溶解碘化鈉（Nal) 0.045g、1·丙 •30- 1380494 . 基-2,3-二甲基咪唑碘化物1.1 lg、碘（I2 ) 0· 1 lg、4·特-丁 基吡啶0.081g，調製電解質組成物。 接著，將由如此作爲所調製之電解質組成物，使用分 配器而塗佈於對極側的表面全面，浸含於其對極，多孔質 絕緣層及色素增感半導體層的內部，從此等對極，多孔質 絕緣層及色素增感半導體層滲出之多餘的電解質組成物係 乾淨地擦拭。 β 接著，於設置在由FTO玻璃基板的兩端之FTO膜所 成之透明導電層上的取出電極接合部分，將尺寸爲60mm x3mm，厚度爲30/zm之鈦箔，經由超音波焊接法加以接 合，作爲取出電極6，7» 接著，於蒸鍍鋁之氣體阻障薄膜之貼合面，將作爲黏 接層而接合熱熔樹脂之保護薄膜，切割成70mmx56mm的 尺寸，經由將此，於色素增感光電變換元件側的面，在減 壓下進行熱壓之時，得到色素增感型光電變換裝置。 • 接著，將由如此作爲形成色素增感光電變換元件模組 之厚度4mm之玻璃基板的背面，經由面模硏磨及光學硏 磨加以依序研磨，作爲厚度0.1mm之薄膜玻璃基板。 接著，於色素增感光電變換元件模組的光入射側的面 ，即薄膜玻璃基板的背面，貼上切割成70mmx56mm之尺 寸的旭硝子製AR薄膜（商品名「ARCTOP」），在從薄 膜玻璃基板露出的部份，與黏接於色素增感光電變換元件 側之上述保護薄膜，經由熱壓而接合，被覆薄膜玻璃基板 -31 - 1380494 經由以上的工程，得到作爲目的之色素增感光電變換 元件模組。其色素增感光電變換元件模組乃8條串聯地連 接5mmx40mm之尺寸的色素增感光電變換元件者。 實施例2 使用於作爲強化玻璃處理之厚度O.lmm之薄膜玻璃 基板上，將與實施例1之FTO膜同樣圖案之ITO (厚度 45 0nm ) / ΑΤΟ (厚度50nm )之透明導電層，經由濺鍍而 形成者，除未進行薄膜玻璃基板的背面硏磨以外，係與實 施例1同樣作爲而製作色素增感光電變換元件模組。 (比較例1 ) 除未進行玻璃基板的背面硏磨，而將玻璃基板的厚度 維持作爲〇.4mm之情況以外，係與實施例1同樣作爲而 製作色素增感光電變換元件模組。 (比較例2) 未於薄膜玻璃基板的―背面，作爲保—護—薄S而形成—AR 薄膜，而於厚度O.lmm之薄膜玻璃基板上，被覆相同厚 度O.lmm之薄膜玻璃基板，對於色素增感光電變換元件 側的面，亦未形成保護薄膜之外，係與實施例2樣作爲而 製作色素增感光電變換元件模組。 (比較例3) -32- 1380494 . 作爲透明導電性基板而使用於聚對苯二甲酸二乙酯（ PEN)薄膜上，蒸鍍ITO膜之塑料薄膜（薄片阻抗20Ω / □，尺寸爲 60mmx46mm，厚度 0. 125mm)，將其 ITO 膜，經由蝕刻加以圖案化，於之間呈形成0.5mm寬度的 間隙地形成9條條紋狀的圖案。之後，依序使用丙酮，醇 ，鹼系洗淨液，超純水，進行超音波洗淨，使其充分乾燥 〇 • 於除了其PEN/ ITO基板之9條ITO膜之中的末端的 1條之8條的ITO膜上，作爲氧化鈦塗漿，使用低溫成膜 用氧化鈦塗漿（Peccell Technologies製），以寬度 5mm ，長度40mm之條紋狀，8條（總面積16cm2)、由刮塗 法加以塗佈。將此膜乾燥後，以1 5 0 °C 3 0分鐘保持在加熱 板上。由如此作爲，多孔質Ti02層。 接著，將使用市售的Ti02粒子（粒徑200nm )，萜 品醇及乙基纖維素而調製之網版印刷用Ti02塗漿，以長 Ιί 度4lmm、寬度5.5mm、厚度10ym塗佈於上述多孔質 Ti02層上。使其Ti02塗漿乾燥，將作爲對極而使用市售 之碳黑與石墨粒子’萜品醇及乙基纖維素而調製之網版印 刷用塗紫’以長度40mm、寬度6mm、厚度30ym塗佈於 上述Ti〇2層上，在使其塗漿乾燥後，以4501，30分鐘 由電器爐加以燒成。使其Ti02塗漿乾燥，將作爲對極而 使用巾售之碳黑與石墨粒子’廠品醇及乙基纖維素而調製 之網版印刷用塗漿，以長度40mm、寬度6mm、厚度30//m 塗佈於上述TiCh層上，在使其塗漿乾燥後，以15〇 〇c， -33- 1380494 3 0分鐘由電器爐加以燒成。如此作爲而形成多孔質絕緣 層及多孔質的對極。 接著，於0.5mM順式雙（異氰硫基）-Ν，Ν-雙（2,2’-吡啶-4,4’-二羧酸）釕（II )二四丁基銨鹽（Ν719色素） 之tert-丁醇/乙腈混合溶劑（體積比1:1)，室溫下， 進行48小時浸漬，於多孔質Ti02層，載持色素。將由如 此作爲載持色素之多孔質Ti02層，以乙腈加以洗淨，在 暗處使其乾燥。由如此作爲，製作色素增感多孔質Ti02 層。 於r-丁内酯3g，溶解碘化鈉（Nal) 0.045g、1-丙 基-2,3-二甲基咪唑碘化物l.llg、碘（I2) O.llg、4-特-丁 基吡啶0.081g，調製電解質組成物。 接著，將由如此作爲所調製之電解質組成物，使用分 配器而塗佈於對極側的表面全面，浸含於其對極，多孔質 絕緣層及色素增感半導體層的內部，從此等對極，多孔質 絕緣層及色素增感半導體層滲出之多餘的電解質組成物係 乾淨地擦拭。 接著，於設置在由PEN"/ ITO g板的Μ端之ϊϊ〇Κ 成之透明導電層上的取出電極接合部分，將尺寸爲 60mm x3mm，厚度爲30//m之駄箱，經由超音波焊接法加以接 合，作爲取出電極。 接著，於蒸鍍鋁之氣體阻障薄膜之貼合面，將作爲黏 接層而接合熱熔樹脂之保護薄膜，切割成70mmx56mm的 尺寸，經由將此，於色素增感光電變換元件側的面，在減 -34- 1380494 壓下進行熱壓之時，將色素增感光電變換元件模組之色素 增感光電變換元件側的表面，經由保護薄膜而完全被覆。 經由以上的工程，得到作爲目的之色素增感光電變換 元件模組。其色素增感光電變換元件模組乃8條串聯地連 接5 mm x4 Omm之尺寸的色素增感光電變換元件者。 對於如以上製作之實施例1〜2及比較例1〜3之色素 增感型光電變換元件模組，測定在AM 1 · 5 ( 1 s un )照射條 件下之光電變換效率。另外，進行測定結束後之色素增感 光電變換元件模組的彎曲試驗，算出產生斷裂前之曲率半 徑。將其結果示於表1。 [表1] 光電變換效率％ 最小曲率半徑（mm) _重量(g) 實施例1 6.71 7.3 1.69 實施例2 6.55 5.9 1.72 實施例3 6.65 7.5 1.20 比較例1 6.80 未彎曲之故無法測定 28.6 比較例2 6.66 23.1 1.45 比較例3 1.29 3.1 (產生薄膜的剝離） 1.50 比較例4 6.51 9.8 1.14 *資料係全由樣品數5而製作的的平均値 從表1知道實施例1，2之色素增感光電變換元件模 組，光電變換效率優越，最小曲率半徑小，輕量％。比較 例1係玻璃基板的厚度爲4mm厚之故，光電變換效率爲 高，但色素增感光電變換元件模組未彎曲，曲率半徑係無 法測定之外，重量極重。比較例2係光電變換效率爲高， 但比較於實施例1，2，曲率半徑極大。比較例3乃未使 -35- 1380494 用薄膜玻璃基板，而使用PEN/ I TO基板，製作色素增感 光電變換元件模組的例，於多孔質Ti02層之形成時，未 歷經500 °C之燒成工程之故，光電變換效率極低。 接著’對於根據本發明之第2實施型態的色素增感光 電變換元件模組加以說明。 如圖6所示，在其色素增感光電變換元件模組，係於 薄膜玻璃基板1的背面未黏接有保護薄膜11，而將黏接 於色素增感光電變換元件的面之保護薄膜9，折回在薄膜 φ 玻璃基板1之端面，接合於薄膜玻璃基板1的背面。其色 素增感光電變換元件模組之其他的構成係與根據第1實施 型態之色素增感光電變換元件模組同樣。 其色素增感光電變換元件模組之製造方法，係除了於 薄膜玻璃基板1的背面未黏接有保護薄膜11，而將保護 薄膜9，折回在薄膜玻璃基板1之端面情況以外，與根據 第1實施型態之色素增感光電變換元件模組之製造方法同 樣。 · 如根據其第2實施形態，可得與第1實施形態相同的 優ιΓ。 對於其色素增感光電變換元件模組之實施例加以說明 實施例3 於薄膜玻璃基板的背面未黏接有AR薄膜，而將黏接 於色素增感光電變換元件側的面之保護薄膜，折回在薄膜 -36- 1380494 玻璃基板之端面’接合於薄膜玻璃基板的背面之情況以外 ，係與實施例1同樣作爲而製作色素增感光電變換元件模 組。 (比較例4 ) 將黏接於色素增感光電變換元件側的面之保護薄膜的 尺寸，作爲較薄膜玻璃基板尺寸（60mmx46mm)爲小之 φ 58mmx44mm -而薄膜玻璃基板的端面呈露出地黏接其保 護薄膜情況以外，係與實施例3同樣作爲而製作色素增感 光電變換元件模組。 對於如以上製作之實施例3及比較例4之色素增感型 光電變換元件模組，測定在AM 1 · 5 ( 1 sun )照射條件下之 光電變換效率。另外，進行測定結束後之色素增感光電變 換元件模組的彎曲試驗，算出產生斷裂前之曲率半徑。將 其結果示於表1。 • 從表1知道實施例3之色素增感光電變換元件模組， 光電變換效率優越，最小曲率半徑小，輕量者。比較例4 係光電變換效率高，保護薄膜的尺寸乃較薄膜玻璃基板的 尺寸爲小，薄膜玻璃基板的端面，因未經由保護薄膜所被 覆之故，比較於實施例3，曲率半徑爲大^ 接著，對於根據本發明之第3實施型態的色素增感光 電變換元件模組加以說明。 如圖7所示，對於其色素增感光電變換元件模組，對 極 5 係於包含選自 Ti、Ni、Cr、Fe、Nb、Ta、W、Co& -37- 13804941380494 IX. Description of the Invention [Technical Fields of the Invention] The present invention relates to a dye-sensitized photoelectric conversion element module and a method of manufacturing the same, and a photoelectric conversion element module, a method of manufacturing the same, and an electronic device, for example, using a carrier dye The dye-sensitized solar cell module of the dye-sensitized semiconductor layer formed by the semiconductor fine particles and various electronic devices are suitable and optimally constructed. [Prior Art] When a fossil fuel such as stone carbon or petroleum is used as an energy source, carbon dioxide generated as a result of this will cause warming of the earth. In addition, the use of atomic energy is accompanied by the risk of contamination through radiation. As far as environmental issues are concerned, there are many major problems with the dependence on these energy sources. On the other hand, the solar energy cell of the photoelectric conversion device that converts sunlight into electric energy uses sunlight as an energy source, and has little influence on the global environment, and is expected to be further popularized. There are various types of materials for solar cells, but most of them are commercially available ''s composition', and these are roughly classified into single crystal or polycrystalline ruthenium crystal lanthanide solar cells, and amorphous ( Amorphous) lanthanide solar cells. Conventionally, for solar cells, single crystal or polycrystalline germanium, that is, crystalline germanium, has been used. However, 'in the crystal sand-based solar cell, the light conversion efficiency showing the performance of converting light (solar) energy into electric energy is higher than that of the amorphous 矽Sun-5-3380494 battery, but it requires a lot of energy for crystal growth. As time goes by, productivity will become lower and it will be disadvantageous on the cost side. In addition, the 'amorphous lanthanide solar cell' has a higher light absorption than the crystalline lanthanide solar cell. The substrate has a wide selection range and is easy to be large-area. However, the light conversion efficiency is lower than that of the crystalline lanthanide solar cell. . Further, the productivity of the 'amorphous lanthanide solar cell' is higher than that of the crystalline lanthanide solar cell. However, similarly to the crystallization-based solar cell, vacuum processing is required at the time of production, and the burden on the device surface is still considerable. . On the other hand, the cost of solar cells is lower, and many solar cells using organic materials instead of sand materials are used. However, the light conversion efficiency of the solar cell is very low below 1%, and there is a problem with durability. In this case, an inexpensive solar cell using a semiconductor sensitized by a dye as an example is reported (refer to Nature, 3 5 3, p. 737-740, 1991). This solar cell is a wet type solar cell which is a photoelectrode, that is, an electro-chemical photo-plasma, which uses a ruthenium complex for a sensitizing dye and is a spectroscopic sensitized titanium oxide porous film. The advantages of the dye-sensitized solar cell are the same as those of the broad visible light wavelength range up to 800 nm, and the quantum efficiency of the photoelectric conversion is high, high energy conversion. Efficiency. In addition, vacuum processing is not required for manufacturing, and large equipment and the like are not required. In addition, the dye-sensitized solar cell system has "perspective", "flexibility", and "brightness", and has not been conceived in the past, and has become a focus in the world. -6- 1380494 In recent years, In the dye-sensitized solar cell module, the development of a flexible solar cell module using a plastic substrate as a supporting substrate has been actively carried out. However, in the manufacturing process of a general dye-sensitized solar cell module, in order to form a baking process of the porous semiconductor layer used for the dye-sensitized semiconductor layer, as described above, a plastic substrate is used as a supporting substrate. In the case of the heat-resistant temperature (glass transition temperature) of the plastic substrate, only the heating temperature of the firing can be raised to 150 ° C. Therefore, the crystallinity of the obtained porous semiconductor layer or the bonding between particles The state is deteriorated, and in this state, the electronic conductivity is low, and the dye-sensitized solar cell module using a plastic substrate is used. In the case of using a glass substrate, the electrical efficiency is reduced by half or more. Therefore, as a problem to be solved by the present invention, it is possible to provide a lightweight and thin structure to constitute flexibility, and high power generation efficiency can be obtained. A dye-sensitized photoelectric conversion element module such as a dye-sensitized solar cell module, a method for producing the same, and an electronic device using the above-described superior dye-sensitized photoelectric conversion element module. More generally, it is possible to provide a photovoltaic system including a dye-sensitized solar cell module or a tantalum solar cell, which can be configured to be flexible and lightweight, and which can provide high power generation efficiency. A conversion element module, a method of manufacturing the same, and an electronic device using the above-described superior photoelectric conversion element module. SUMMARY OF THE INVENTION 1380494 In order to solve the above problems, the first invention belongs to a support substrate and has a plurality of dye sensitizations. a dye-sensitized photoelectric conversion element module of a photoelectric conversion element, which is characterized as the support substrate Use thickness 〇. In the film glass substrate of 2 mm or less, a resin-based protective film having a size larger than the size of the film glass substrate is adhered to at least one surface of the dye-sensitized photoelectric conversion element module. In the first invention, when a thin film glass substrate is used as a support substrate, when the porous semiconductor layer used for the dye-sensitized semiconductor layer is formed, for example, it can be subjected to a baking treatment at a high temperature of about 500 °C. Therefore, the crystallinity of the porous semiconductor layer or the bonding state of the particles is improved, and high power generation efficiency can be obtained from the case where high electron conductivity can be obtained. In addition, the thickness is 0. The film glass substrate of 2 mm or less can be easily bent in the same manner as the plastic substrate, and is not only flexible but also lightweight. The thinner the thickness of the thin film glass substrate, the easier it is to bend. Although it is related to light weight, the thickness is too small, and the mechanical strength is too low. From this point of view, there is a desired thickness, specifically, 〇. 〇1~〇. 2mm is preferred. Its thickness is 0. A film having a thickness of 2 mm or less may be produced by a glass substrate which is thinned by a thinner substrate, or a thin film glass substrate which is made to have a thickness from the beginning. The material of the thin film glass substrate is not particularly limited, and various conventionally known ones can be used, and an appropriate selection can be made therefrom. The thin film glass substrate is also necessary to increase the mechanical strength by strengthening the vitrification. On the other hand, when the thickness is 0. When the thickness is 2 mm or less, the thin film glass -8 - 1380494 substrate is attached to the surface or the end surface, and when there is a slight crack or damage, it is likely to be broken. That is, the mechanical strength of the thin film glass substrate is not dependent on the smoothness of the surface or end surface of the thin film glass substrate. Therefore, in order to prevent breakage of the thin film glass substrate and prevent the dye-sensitized photoelectric conversion element module from being prevented, at least one surface of the dye-sensitized photoelectric conversion element module is desirably two-sided, and the size of the thin film glass substrate is adhered. A resin-based protective film of the above size. By coating the entire surface of at least one of the dye-sensitized photoelectric conversion element modules via the protective film, it is possible to greatly improve the mechanical strength of the bending of the dye-sensitized photoelectric conversion element module. The breakage of the thin film glass substrate is drastically reduced, and the destroyer of the dye-sensitized photoelectric conversion element module can be prevented. In order to further improve the mechanical strength of the curved dye-sensitized photoelectric conversion element module, it is preferable that at least a part of the end surface of the film-coated glass substrate is coated as much as possible by the protective film. Therefore, in the case of the surface-bonding protective film which is only one of the dye-sensitized photoelectric conversion element modules, it is preferable to fold the protective film to cover the end face of the thin film glass substrate, and to improve the photoreceptor element of the thin film. When the protective film is bonded to both sides, the portions of the protective film exposed from the film glass substrate are bonded to each other, and the end faces of the film glass substrate are preferably coated. The protection of the end surface of the thin film glass substrate is preferably performed on the entire outer periphery of the thin film glass substrate. The thin film glass substrate has a polygonal shape, and the curved side is determined to be one side or more, and at least one side is covered. The end face is better. The protective film and the adhesive which are adhered to the surface on the light incident side of the dye-sensitized photoelectric conversion element module are made of a transparent structure. -9- 1380494 In the plural range of the dye-sensitized photoelectric conversion element module 'typically' on the thin film glass substrate, each having a transparent conductive layer 'on its transparent conductive layer, sequentially stacking the dye-sensitized semiconductor The layer 'porous insulating layer and the counter electrode constitute a dye-sensitized photoelectric conversion element' on the surface of the dye-sensitized photoelectric conversion element module on the side of the dye-sensitized photoelectric conversion element, and the protective film is coated with a protective film. Increase the photoelectric conversion element. In the case where a plurality of dye-sensitized photoelectric conversion elements are connected in series to each other on a thin film glass substrate, a portion of the dye-sensitized photoelectric conversion elements adjacent to each other is electrically connected to each other. The transparent conductive layer of the photosensitive conversion element is added to the opposite pole of the other dye-sensitized photoelectric conversion element. The dye-sensitized semiconductor layer and the porous insulating layer are typically applied to the dye-sensitized semiconductor layer and the porous insulating layer, and the electrolyte is also impregnated with the counter electrode. The transparent conductive layer formed in a plurality of ranges of the thin film glass substrate may be patterned before laminating the dye-sensitized semiconductor layer, the porous insulating layer, and the counter electrode, or may be laminated to the dye-sensitized semiconductor layer and porous. After the insulating layer and the counter electrode, the pattern is formed. The patterning can be carried out by various conventionally known etching methods, laser cutting, physical honing processing, and the like. The lower the surface resistance (sheet resistance) of the transparent conductive layer formed on the thin film glass substrate is preferably. Specifically, the surface resistance of the transparent conductive layer is preferably 500 Ω/□ or less, and more preferably 100 Ω/□. As a material of the transparent conductive layer, a known material can be used, and specifically, indium-tin composite oxide (ITO), fluorine-doped Sn02 (FT0), doped yttrium Sn02 (ΑΤΟ), Sn02, ΖηΟ can be cited. Indium-zinc composite oxide (ΙΖΟ) -10- 1380494, etc., but is not limited thereto, and may be used in combination of two or more kinds. In addition, in order to reduce the surface resistance of the transparent conductive layer forming the transparent conductive layer on the thin film glass substrate, the collection efficiency is improved, and a metal having high conductivity or the like may be additionally disposed on the thin film glass substrate. Wiring made of conductive materials such as carbon. The conductive material used for the wiring is not particularly limited, and the corrosion resistance and the oxidation resistance are high, and the leakage current of the conductive material itself is preferably low. • A dye-sensitized semiconductor layer is typically a porous semiconductor layer formed by holding semiconductor microparticles of a dye. As the material of the semiconductor fine particles, in addition to the elemental semiconductor material represented by ruthenium, various compound semiconductors, compounds having a perovskite structure, and the like can be used. These semiconductor materials are preferably photo-excited, and the conduction band electrons are carriers, and the n-type semiconductor which generates the anode current is preferred. When these semiconductors are specifically exemplified, they are Ti02 'ZnO, W03 'Nb205 'TiSr03, Sn02, etc. Among them, anatase type Ti〇2 is particularly preferable. The type of the semiconductor is not limited to this, and these may be used as a mixture of two or more types. Further, the semiconductor fine particles may be in various forms such as a granular shape, a rod shape, or the like as needed. The particle size of the semiconductor fine particles is not particularly limited, and the average particle diameter of the primary particles is preferably from 1 to 200 nm, more preferably from 5 to 100 nm. Further, semiconductor fine particles having an average particle diameter can be mixed with semiconductor fine particles having an average particle diameter larger than that of the semiconductor fine particles having a large average particle diameter, and the incident light can be scattered by the semiconductor fine particles having a large average particle diameter, thereby improving the quantum yield. . In this case, the average particle diameter of the additionally mixed semiconductor fine particles is preferably 20 to 500 nm -11 - 1380494. The film forming method of the semiconductor layer formed by the semiconductor fine particles is not particularly limited, and in consideration of physical properties, convenience, and manufacturing cost, it is preferable to use a wet filmmaker to uniformly disperse the powder or sol of the semiconductor fine particles in a uniform manner. A method of applying a solvent such as water or an organic solvent to a transparent conductive substrate is preferred. The coating system is not particularly limited in its method, and can be carried out according to a known method, for example, a dipping method, a spray method, a ring bar coating method, a spin coating method, a roll coating method, a knife coating method, and a gravure printing method can be used. The coating method or the like is also used as a wet printing method, and can be carried out, for example, by various methods such as letterpress, offset, gravure, gravure, rubber, and screen printing. In the case where crystalline titanium oxide is used as the material of the semiconductor, the crystalline anatase type is preferably from the point of photocatalytic activity. The anatase type titanium oxide may be in the form of a commercially available powder, sol or slurry, or a known method of decomposing a titanium alkoxide or the like by adding water to form a specific particle size. When a commercially available powder is used, it is preferred to release the secondary agglomeration of the particles. In the preparation of the coating liquid, it is preferred to use a mortar, a ball mill, or an ultrasonic dispersing device to pulverize the particles. In this case, in order to prevent re-agglomeration of the secondary aggregation particles, ethyl acetonide, hydrochloric acid, citric acid, an interfacial detergent, a chelating agent, or the like may be added. Further, in order to increase the viscosity, a polymer such as polyoxyethylene or polyvinyl alcohol, a tackifier such as a cellulose-based tackifier, or the like may be added, and a semiconductor layer formed of semiconductor fine particles, in other words, a semiconductor The microparticle layer is preferably a sensitizing dye which can absorb a large amount of particles, and the surface area is large. For this reason, the surface area of -12 to 1380494 in which the semiconductor fine particle layer is coated on the support is preferably ίο or more for the projected area, and more preferably 100 or more. Although this upper limit is not particularly limited, it is 1,000 times. In general, the semiconductor fine particle system has an increased thickness, and the amount of the dye contained per unit of projected area increases, so that the extraction rate becomes higher, but the diffusion distance of the injected electron increases, and the charge recombination is lost. It has also become bigger. Accordingly, although the semiconductor fine particles are preferably thick, the thickness thereof is generally 〇_1 to 100// more preferably 1 to 50/m, and more preferably 3 to 30/m. After the semiconductor microlayer is coated with the support, the particles are electrically contacted to increase the strength of the film or to improve the adhesion to the substrate. The firing temperature is not particularly limited, and the temperature is excessive. When it is high, the resistance will become higher, and more, there will be melting, usually 4 (TC, ° C is better, more preferably 40 ° C ~ 65 0 ° C. In addition, the firing time is not limited Usually, it is 1 〇 minute to 1 〇 hour. After firing, in order to increase the surface area of the bulk particle layer, for the purpose of increasing the necking between the semiconductor fine particles, for example, trichlorochloride can be used for chemical plating using an aqueous solution of titanium tetrachloride. The necking treatment of the titanium-titanium aqueous solution or the impregnation treatment of the conductor titanium oxide ultrafine particle sol having a diameter of 1 Onm or less. For example, the dye which is carried on the semiconductor layer is not particularly limited as long as it exhibits sensitization. List the rhodamine pigments such as rhodamine B, rose, blush, erythromycin, etc., merocyanine, cryptophyll pigment, phenolic saffron, capriline blue, thiosinil, methylene Salt-based dyes, chlorophyll, zinc bismuth Further, the porphyrin-based compound such as magnesium porphyrin is preferably a azo dye or a phthalocyanine system, and is generally lighter in color, and is preferably a sub-layer m or a particle. Under semi-conducting, or half-acting rhododendron, such as blue-and-white comonomer-13- 1380494, coumarin compound, Ru bipyridyl compound, Ru-tripyridyl compound, lanthanide pigment, polycyclic lanthanide In particular, the quantum yield of the Ru bipyridyl compound is particularly high among these, but the sensitizing dye is not limited thereto, and may be increased. The sensitizing dye is used as a mixture of two or more kinds. The method of absorbing the semiconductor layer applied to the dye is not particularly limited, and the sensitizing dye may be dissolved, for example, in an alcohol, a nitrile or a nitromethane. , halogenated hydrocarbons, ethers, dimethyl hydrazine, decylamines, N-methylpyrrolidone, 1,3-dimethylimidazolidinone, 3-methyloxazolidinone, esters, carbonates a solvent such as a ketone, a hydrocarbon, or a water, and the semiconductor layer is impregnated thereon. Alternatively, the dye solution may be applied to the semiconductor layer, and in the case of using a dye having a high acidity, defosic acid or the like may be added to reduce the convergence between the dyes. After the sensitizing dye is absorbed, excessive adsorption is promoted. For the purpose of removing the sensitizing dye, an amine may be used to treat the surface of the semiconductor electrode. Examples of the amine may include pyridinium, 4-tert-butylpyridine, polyvinylpyrrolidone, etc., which are liquid. The condition may be used as it is, or it may be dissolved in an organic solvent. · The material of the porous insulating layer is not electrically conductive, and is not particularly limited, but the special use includes a selected from Zr, Ab. An oxide of at least one element selected from the group consisting of Ti, Si, Zn, ..., and Nb, wherein an oxide used, in which an oxidation pin, alumina, titania, cerium oxide or the like is used, is preferable. Typically, ruthenium particles are used. The porosity of the porous insulating layer is preferably 10% or more. The upper limit of the porosity of -14 to 1380494 is not limited, and the viewpoint of the physical strength of the porous insulating layer is usually from 10 to 80%. When the porosity is 10% or less, the influence on the diffusion of the electrolyte is markedly deteriorated, and the characteristics of the dye-sensitized photoelectric conversion element module are remarkably lowered. Further, the pore diameter of the porous insulating layer is preferably 1 to 10 nm. When the pore diameter is less than 1 nm, the influence on the diffusion or the pigment of the electrolyte is lowered, and the characteristics of the dye-sensitized photoelectric conversion element module are degraded. Further, when the pore diameter is larger than 100 nm, the catalyst particles of the opposite pole are intruded into the porous insulating layer, and a short circuit is generated. The method for producing the porous insulating layer is not limited, but the sintered body of the above oxide particles is preferred. The material of the counter electrode is not particularly limited, and the material having the catalytic activity itself is electrically conductive and can be used as it is. When the catalyst itself is not electrically conductive, the conductive substance and the catalytic activity can be combined. The substance and the user. Specifically, for example, it is preferable that the polar group contains at least one element selected from the group consisting of Pt, Ru, Ir, and C, and those containing Pt or C are preferable, and an anthrax containing C material in particular is preferable. It is ideal for cheap reasons. The single layer on the side of the porous insulating layer of the foil formed of a metal or an alloy may have a catalyst layer or may be formed of a foil formed of a catalytically active material. By doing so, it is possible to thin the constituent poles, and it is possible to reduce the thickness and weight of the dye-sensitized photoelectric conversion element module. Further, the material of the foil constituting the counter metal or the alloy and the material having the catalyst layer are selected in such a manner that there is no limitation on the material surface of the counter electrode. Further, since the dye-sensitized semiconductor layer and the counter electrode are separated by the porous insulating layer, it is possible to prevent the pigment of the -15-1380494 dye-sensitized semiconductor layer from adhering to the extremes without deterioration of characteristics. The foil formed by the metal or alloy of the counter electrode is made of a metal or an alloy containing at least one type of element selected from the group consisting of Ti, Ni, Cr, Fe, Nb, Ta, W, Co, and Zr. The foil is better. The catalyst layer provided on one side of the porous insulating layer side of the foil formed of the metal or alloy, or the material having the catalyst layer contains at least one selected from the group consisting of Pt, Ru, Ir, and C. The element is better. From the viewpoint of the reduction in the thickness of the dye-sensitized photoelectric conversion element module, the thickness of the electrode, that is, the total thickness of the foil and the catalyst layer formed by the metal or alloy or the thickness of the foil formed by the material having the catalyst layer is 0. . Those below 1mm are preferred. For carrying a catalyst layer on a foil formed of a metal or an alloy, a method of wet coating a solution containing a catalyst or a precursor of a catalyst, or a sputtering method, a vacuum evaporation method, or a chemical gas may be used. Dry method such as phase growth (CVD), etc. In this case, the counter electrode and the transparent conductive layer may be directly bonded to each other or may be joined by a conductive material. In the latter case, specifically, the counter electrode and the transparent conductive layer are bonded to each other, for example, via a conductive adhesive or a low melting point metal or alloy having a melting point of 300 ° C or less. As the conductive adhesive, 'commercially available silver, carbon, nickel, copper paste or the like can be used. An anisotropic conductive adhesive or a film can also be used. Further, various low-melting point metals or alloys such as In or In-Sn-based solder which can be bonded to the transparent conductive layer can be used. Further, in the case where the joint portion between the counter electrode and the transparent conductive layer is in direct contact with the electrolyte, it is also possible to prevent contact with the electrolyte by protecting the joint portion with a resin or the like. The material of the protective film is, for example, a resin type, and is not particularly limited. However, it is preferable to use a material having high gas barrier properties. Specifically, for example, -16 - 1380494 uses an oxygen permeability of 1 〇〇 (cc/ Below m2/day/atm), the water vapor transmission rate is 1 〇〇 (g/ m2/day) or less. For the protective film, for example, a gas barrier film represented by a food exterior film or the like is used, and at least one type of gas selected from the group consisting of aluminum, cerium oxide and aluminum oxide is preferably used. a gas barrier film of a barrier material, and the like. The protective film is preferably sealed by using a suitable adhesive under reduced pressure or in an inert gas atmosphere. The dye-sensitized photoelectric conversion of the dye-sensitized photoelectric conversion element module is provided by such a protective film. When the surface on the element side or the back side of the thin film glass substrate is prevented from being impregnated with oxygen or the like from the outside, the gas or water vapor is equal to the inside of the dye-sensitized photoelectric conversion element module, so that deterioration of characteristics such as photoelectric conversion efficiency can be suppressed. Further, it is possible to improve the durability of the dye-sensitized photoelectric conversion element module. The material of the adhesive layer to be used for the adhesion of the protective film is not particularly limited, but the gas barrier property is high, and the material which is chemically inactive and electrically insulating is preferable. Specifically, a resin can be used. , glass frit, etc., more specifically, for example, various ultraviolet (UV) curing resins such as epoxy resin, urethane resin, polyoxyn resin, acrylic resin, various thermosetting resins, and hot melt resins can be used. 'Low melting glass frit, etc. It is preferable that the adhesive layer and the protective film are integrated, but it is not limited thereto. The electrolyte is used in addition to the combination of iodine (12) with metal iodide or organic iodide 'bromo(Br2) and metal bromide or organic bromide'. It is possible to use ferritic cyanate/ferrocyanate or ferrocene. A metal complex such as iron/iron tin ion, a sulfur compound such as polysulfide sodium, an alkylthiol group/alkyl disulfide, a violet pigment, hydroquinone/hydrazine, and the like. The cation of the metallized-17-1380494 compound is Li, Na, K, Mg, Ca, Cs, etc., and the cation as an organic compound is a tetraalkyl-based compound such as a tetraalkyl-based group, a pyridinium or an imidazole. It is preferable, but it is not limited to this, and it is also possible to mix two or more of these. Among them, an electrolyte of the combination of 12 and a quaternary ammonium compound such as Lil, Nal or an imidazolium iodide salt is preferred. The concentration of the electrolyte salt is preferably 〇·〇5Μ~10M, more preferably 0. 2M~3M. The concentration of 12 or Br2 is preferably 0. 0005Μ~1Μ, more preferably 0. 001Μ~0. 3Μ. Further, for the purpose of increasing the open voltage, an additive made of an ammonia compound represented by 4-tert-butylpyridine may be added. Examples of the solvent constituting the electrolytic solution include water, alcohols, ethers, esters, carbonates, lactones, carboxylates, phosphotriesters, heterocyclic compounds, nitriles, and ketones. Amines, nitromethane, halogenated hydrocarbons, dimethyl sulfoxide, Cyclopentane, Ν-methylpyrrolidone, 1,3-dimethylimidazolidinone, 3-methyloxazolidinone, hydrocarbon In addition, the present invention is not limited thereto, and two or more of these may be used in combination. Further, as a solvent, an ionic liquid of a tetraalkyl-based, pyridine-based or imidazole-based fourth-order ammonium salt can also be used to reduce dye-sensitized photoelectric conversion_component-drain-liquid,-"tooth-liquid deficiency For the purpose of bursting, the inorganic electrolyte particles may be dispersed in the electrolyte composition, dissolved in a gelling agent, a polymer, or a crosslinking monomer, and used as a gel electrolyte. When the ratio of the gel matrix to the electrolyte composition is as large as the electrolyte composition, the ionic conductivity becomes high, but the mechanical strength decreases. Conversely, when the electrolyte composition is too small, the mechanical strength is large, but the ionic conductivity is large. For the reason of the decrease, the electrolyte composition is desirably 50 to 99 wt% of the gelatinous electric-18-18380494, and more preferably 80 to 97 wt%. Further, by dissolving the above electrolyte and a plasticizer in a polymer and volatilizing a plasticizer, it is also possible to realize an all-solid type dye-sensitized photoelectric conversion element module. The method for producing the dye-light-sensitized photoelectric conversion element module is not particularly limited, but in consideration of the thickness, productivity, pattern accuracy, and the like of each layer, the porous insulating layer and the opposite pole are used for the semiconductor layer before the dye is absorbed. And the contact layer, and even if the counter electrode has a catalyst layer, the catalyst layer is preferably formed by a wet coating method such as screen printing or inkjet coating, especially via a screen. It is better to form by printing. It is preferred that the semiconductor layer and the porous insulating layer before the dye absorption are formed by baking with a coating containing particles constituting each layer. The respective porosity is determined by the ratio of the viscous composition of the paste to the particles. In the same manner, it is preferable to form the counter electrode by the coating of the paste, and it is preferable to form the semiconductor layer and the porous insulating layer at the stage of forming the semiconductor layer and the porous insulating layer. The layer absorbs the dye and then forms a counter electrode on the porous insulating layer. When a single layer on the side of the porous insulating layer of the foil formed of a metal or an alloy has a catalyst layer, the opposite layer is formed, and the catalyst layer on the box formed by the metal or alloy is made porous. The layer 'joins the transparent conductive layer of the adjacent dye-sensitized photoelectric conversion element. The charge of the electrolyte such as the dye-sensitized semiconductor layer or the porous insulating layer of each of the dye-sensitized photoelectric conversion elements can be carried out, for example, by a method such as a phenol dispenser or a printing ink jet. However, 'in the dye-sensitized photoelectric conversion element module in which a plurality of dye-sensitized photoelectric conversion elements are connected in series, a short circuit occurs between the dye-sensitized photoelectric conversion elements by flowing out the electrolyte. 1380494 It is preferable to dope the amount of the electrolyte contained in an amount of the dye-sensitized semiconductor layer or the porous insulating layer of each of the dye-sensitized photoelectric conversion elements. The dye-sensitized photoelectric conversion element module can be produced in various shapes in accordance with the application, and the shape is not particularly limited. The dye-sensitized photoelectric conversion element module is typically configured as a dye-sensitized solar cell module. However, the dye-sensitized photoelectric conversion element module is, in addition to the dye-sensitized solar cell module, for example, a dye-sensitized sensor. According to a second aspect of the invention, there is provided a method of producing a dye-sensitized photoelectric conversion element module comprising a plurality of dye-sensitized photoelectric conversion elements on a support substrate, wherein the thickness of the support substrate is 〇. a thin film glass substrate of 2 mm or less, wherein the plurality of dye-sensitized photoelectric conversion elements are formed on the thin film glass substrate, and a dye-sensitized photoelectric conversion element module is formed, and at least one of the dye-sensitized photoelectric conversion element modules is formed. The surface of the film is bonded to a resin-based protective film having a size larger than the above-mentioned thin film glass substrate. In the method for producing a dye-sensitized photoelectric conversion element module, typically, when a dye-sensitized semiconductor layer, a porous insulating layer, and a counter electrode are formed on a transparent conductive layer, a dye-sensitized photoelectric conversion element is formed. a portion of the two adjacent dye-sensitized photoelectric conversion elements electrically connected to one of the transparent conductive layers of the dye-sensitized photoelectric conversion element and the other one of the dye-sensitized photoelectric conversion elements Right. -20-l38〇494 In the second invention, the case other than the above is not related to the nature of the invention, and is described in connection with the first invention. According to a third aspect of the invention, in the electronic device using the dye-sensitized photoelectric conversion element module, the dye-sensitized photoelectric conversion element module belongs to a support substrate, and has a dye-sensitized photoelectric conversion of a plurality of dye-sensitized photoelectric conversion elements. The component module is characterized in that the thickness of the support substrate is 0. In the film glass substrate of 2 mm or less, a resin-based protective film having a size larger than the size of the film glass substrate is adhered to at least one surface of the dye-sensitized photoelectric conversion element module. The electronic device can basically be configured in any way, including both a portable type and a built-in type. However, when a specific example is given, there are mobile phones, mobile devices, robots, personal computers, in-vehicle devices, various home electrical appliances, and the like. . In this case, the dye-sensitized photoelectric conversion element module is, for example, a dye-sensitized solar cell module used as a power source for such an electronic device. In the third invention, the case other than the above is not related to the nature of the invention, and is described in connection with the first invention. According to a fourth aspect of the invention, a photoelectric conversion element module having a plurality of photoelectric conversion elements on a support substrate is characterized in that the thickness of the support substrate is 0. A thin-film glass substrate of 2 mm or less is bonded to a surface of at least one of the above-mentioned dye-sensitized photoelectric conversion element modules, and a protective film of a resin having a size of the above-mentioned thin film glass substrate of a size of -21 - 1380494 is adhered. According to a fifth aspect of the invention, a method of manufacturing a photoelectric conversion element module having a plurality of photoelectric conversion elements on a support substrate, wherein: the thickness of the support substrate is 0. a thin film glass substrate of 2 mm or less, wherein the plurality of photoelectric conversion elements are formed on the thin film glass substrate, and the photoelectric conversion element module is formed, and the surface of at least one of the photoelectric conversion element modules is bonded thereto. A resin-based protective film of a size larger than the size of a thin film glass substrate. According to a sixth aspect of the invention, in an electronic device using a photoelectric conversion element module, the photoelectric conversion element module belongs to a support substrate, and a photoelectric conversion element module having a plurality of photoelectric conversion elements is characterized as the support substrate And the thickness is 0. In a film glass substrate of 2 mm or less, a resin-based protective film having a size larger than the size of the film glass substrate is adhered to at least one surface of the photoelectric conversion element module. In the fourth to sixth inventions, the photoelectric conversion element of the photoelectric conversion element is not limited to a dye-sensitized photoelectric conversion element such as a solar cell, and includes a conventionally known photoelectric conversion element such as a tantalum solar cell. In the fourth to sixth inventions, the case other than the above is not related to the nature of the invention, and is related to the third to third inventions. The invention is established as described above, and the thickness is used as a support substrate. -22- 1380494 degrees is 0. A thin film glass substrate of 2 mra or less is flexible and lightweight. In addition, a resin-based protective film having a size larger than the size of the thin film glass substrate is adhered to at least one surface of the dye-sensitized photoelectric conversion element module or the photoelectric conversion element module, and the dye-sensitized photoelectric conversion element module can be obtained. Or an increase in the mechanical strength of the photoelectric conversion element module. In addition, the thin film glass substrate can also withstand heating at a temperature of about 500 °C. Therefore, in the dye-sensitized photoelectric conversion element, when the porous semiconductor layer used for the dye-sensitized semiconductor layer is formed, for example, the firing treatment can be performed at a high temperature of about 500 ° C, and the porous semiconductor layer can be formed. The crystallinity or the state of bonding of the particles becomes good, and high electron conductivity can be obtained, and further high power generation efficiency can be obtained. Further, in the lanthanide photoelectric conversion element, the film formation or heat treatment of the ruthenium film can be carried out at a temperature of up to 50 (a high temperature of TC, whereby a good ruthenium film can be obtained, and high power generation efficiency can be obtained. According to the present invention, it is possible to realize a dye-sensitized photoelectric conversion element module or a photoelectric conversion element module which is flexible and lightweight, and which can obtain high power generation efficiency, and can use its superior dye sensitization. An electronic device that realizes high performance by a photoelectric conversion element module or a photoelectric conversion element module. [Embodiment] Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, in the following embodiments, The same or corresponding parts are denoted by the same reference numerals. -23- 1380494 Fig. 1 to Fig. 3 show a dye-sensitized photoelectric conversion element module according to the first embodiment of the present invention. FIG. 2 is a cross-sectional view of the main portion of the dye-sensitized photoelectric conversion element module, and FIG. 3 is a plan view of the dye-sensitized photoelectric conversion element module. Fig. 1 is a cross-sectional view taken along line XX of Fig. 3, and Fig. 2 is a partially enlarged cross-sectional view taken along line XX of Fig. 3. As shown in Fig. 1 to Fig. 3, in the dye-sensitized type The photoelectric conversion element module is provided with a stripe-shaped transparent conductive layer in parallel on the insulating and transparent thin film glass substrate 1. The thickness of the thin film glass substrate 1 is used as a crucible. 2mm or less, the best is 0. 01~0. 2mm. Each of the transparent conductive layers 2 is sequentially laminated with a dye-sensitized semiconductor layer 3 extending in a stripe shape in the same direction as the transparent conductive layer 2, and the porous semiconductor layer 4 and the counter electrode 5 constitute a dye-sensitized photoelectric conversion. element. At least the entire dye-sensitized semiconductor layer 3 and the porous insulating layer 4 are typically immersed in the dye-sensitized semiconductor layer 3, the porous insulating layer 4, and the entire counter electrode 5 to be impregnated with an electrolyte. In this case, the width of the dye-sensitized semiconductor layer 3 is smaller than that of the transparent conductive layer 2, and a portion adjacent to the longitudinal direction of the transparent conductive layer 2 is exposed. The width of the porous insulating layer 4 is such that the width of the S dye-sensitized semiconductor layer 3 is large, and the entire surface of the coated dye-sensitized semiconductor layer 3 is provided. The end of the porous insulating layer 4 extends along the side surface of one of the dye-sensitized semiconductor layers 3 to be bonded to the thin film glass substrate 1 and the other end is along the other side surface of the dye-sensitized semiconductor layer 3. It extends and is bonded to the transparent conductive layer 2. Further, one end of the counter electrode 5 of one of the dye-sensitized photoelectric conversion elements is bonded to the transparent conductive layer 2 of the adjacent dye-sensitized photoelectric conversion -24-1380494 element. Thus, a plurality of dye-sensitized photoelectric conversion elements are electrically connected in series. 1 and 3' show the case where eight dye-sensitized photoelectric conversion elements are connected in series', but the number of dye-sensitized photoelectric conversion elements connected in series is selected according to necessity, and certainly not Limited to 8. The transparent conductive layer 2 of the dye-sensitized photoelectric conversion element in which one end of the plurality of dye-sensitized photoelectric conversion elements connected in series is formed is connected to the extraction electrode 6 and is adjacent to the dye-sensitized photo formed on the other end. The transparent conductive layer 2 of the conversion element is formed, and the transparent conductive layer 2 at one end of the counter electrode 5 of the dye-sensitized photoelectric conversion element is connected to the extraction electrode 7. The adhesive layer 8 is provided on the entire portion of the counter electrode 5 and the porous insulating layer 4 between the respective dye-sensitized photoelectric conversion elements and the counter electrode 5, and the adhesive layer 8 is entirely bonded and bonded. The thin film glass substrate 1 has a large resin-based protective film 9. On the other hand, an adhesive layer 10 is provided on the entire back surface of the thin film glass substrate 1, and a resin-based protective film 11 having a larger size than the thin film glass substrate 1 is bonded to the entire adhesive layer 10. Further, the protective film 9 and the protective film 11 are bonded to each other from the portions exposed from the thin film glass substrate 1, whereby the end faces of the thin film glass substrate 1 are also covered by the protective film 9. The protective film Π and the protective film 9 which are bonded to the light incident surface side are made of a transparent one. However, the protective film 9 and the adhesive layer 8 may be made transparent, and this may not be the case. Fig. 4 is a plan view showing an enlarged porous insulating layer 4, a portion of the counter electrode 5 and the adhesive layer 8 (a portion surrounded by a dotted line in Fig. 3). The dye-sensitized semiconductor layer 3 is used in a semiconductor fine particle layer or a -25 - 1380494 porous semiconductor layer to carry a dye. At least one of the protective films 9 and 11 is preferably a resin-based foil film made of a gas barrier material, and for example, an oxygen permeability of 100 (cc/m 2 /day/atm) or less and a water vapor permeability are used. L〇〇(g/m2/day) or less. Further, as the protective film 1 1 on the light incident side, in order to control the amount of light loss through the reflected incident light, a non-reflective (AR) film is used. The thin film glass substrate 1, the transparent conductive layer 2, the dye-sensitized semiconductor layer 3, the porous insulating layer 4, the counter electrode 5, and the adhesive layers 8, 10 are selected from the above-described configurations, and may be used as necessary. . Next, a method of manufacturing the dye-sensitized photoelectric conversion element module will be described. First, as shown in Fig. 5A, the thin film glass substrate 1 is prepared, and after the transparent conductive layer 2 is formed on the entire surface of the thin film glass substrate 1, the transparent conductive layer 2 is patterned into stripes by etching. Here, as the thin film glass substrate 1, the initial thickness is 〇. The composition of 2mm or less is also possible, and the thickness can be used. In the case of the latter, the thin film glass substrate 1 is thinned by honing or the like as 0. Thickness of 2 mm_ or less. Further, on each of the transparent conductive layers-2, a coating of H semiconductor fine particles is applied to a specific interval. Next, the thin film glass substrate is heated to a specific temperature, and the semiconductor fine particles are sintered to form a porous semiconductor layer formed by the semiconductor fine particle sintered body. Next, after the porous insulating layer 4 is formed in its entirety, the porous insulating layer 4 is patterned into stripes by etching. Next, the counter electrode 5 is formed entirely on the porous insulating layer 4, and one end ' of the counter electrode 5 is bonded to each of the -26 - 1380494 transparent conductive layers 2. Then, the porous semiconductor layer formed of the semiconductor fine particle sintered body is formed into the porous insulating layer 4 and the thin film glass substrate 1 of the counter electrode 5, and is immersed in a dye solution or the like to form semiconductor fine particles in the porous semiconductor layer. The dye-sensitized semiconductor layer 3 is formed by holding a dye for sensitization. Next, an electrolyte is applied to the surface of the counter electrode 5 side, and at least the entire electrolyte is impregnated into the φ of the dye-sensitized semiconductor layer 3 and the porous insulating layer 4, and is typically immersed in the dye sensitization. The semiconductor layer 3 and the porous insulating layer 4 and the counter electrode 5 are all the same. Next, the respective extraction electrodes 6 are joined to the transparent conductive layer 2 formed by the transparent conductive layer 2 formed of the dye-sensitized photoelectric conversion element having one end and the transparent conductive layer 2 having the other end of the dye-sensitized photoelectric conversion element. Next, as shown in B of FIG. 5, the protective film 9 is adhered to the surface of the counter 5 side by the adhesive layer 8. # Next, the thickness used is thinner as the thin film glass substrate 1. When the thickness of 2 mm is large, the thin film glass substrate 1 is thinned by honing or the like, and the thickness is taken as 〇. 2mm or less. Thereafter, on the back surface of the thin film glass substrate 1, the protective film 11 is adhered by the adhesive layer 1 , and the protective film 11 and the protective film 9 are bonded to the exposed portion from the thin film glass substrate 1 to bond the thin film glass substrate 1 The end face is covered by the protective film 9. As described above, the dye-sensitized photoelectric conversion element module shown in Figs. 1 to 3 was produced. Next, the operation of the dye-sensitized photoelectric conversion element module will be described in -27-1380494. The light that has entered through the thin film glass substrate 1 from the side of the thin film glass substrate 1 excites the dye of the dye-sensitized semiconductor layer 3 to generate electrons. The electrons are rapidly extrapolated from the pigment to the semiconductor fine particles of the dye-sensitized semiconductor layer 3. On the other hand, the dye that has lost electrons receives electrons from the ions of the electrolyte impregnated into the entire dye-sensitized semiconductor layer 3 and the porous insulating layer 4, and the molecules that extrapolate the electrons again receive electrons on the surface of the counter electrode 5. Through a series of reactions, electric power is generated between the transparent conductive layer 2 and the counter electrode 5 electrically connected to the dye-sensitized semiconductor layer 3. Thereby, the photoelectric conversion is performed. In this case, the extraction electrode 6 of the transparent conductive layer 2 of the dye-sensitized photoelectric conversion element connected to one end of the plurality of dye-sensitized photoelectric conversion elements connected in series and the transparent conductive layer of the dye-sensitized photoelectric conversion element connected to the other end Between the extraction electrodes 7 of 2, the total electric power of the electric power of each of the dye-sensitized photoelectric conversion elements is generated. According to the first embodiment, the thickness is 0. Below 2 mm, the best is 〇. 〇1~0. The 2 mm thin film glass substrate 1 and the entire surface of the dye-sensitized photoelectric conversion element and the end surface of the thin film glass substrate 1 are covered by the thin film; the W® body of the film is covered by the protective film 11, and The dye-sensitized photoelectric conversion element module is flexible and thin, and can sufficiently ensure the mechanical strength of the dye-sensitized photoelectric conversion element module. In addition, since the thin film glass substrate 1 is used as the support substrate, the baking treatment at the time of formation of the porous semiconductor layer used for the dye-sensitized semiconductor layer 3 can be performed at a temperature of about 500 ° C. The crystallinity of the porous semiconductor -28-1380494 layer or the state of bonding of the particles is good, and the conductivity can be made good. Therefore, the power generation efficiency of the dye-sensitized photoelectric conversion group can be improved. Further, the film formed of the gas barrier material as the protective films 9, 11 can prevent the penetration of the inside of the module, such as oxygen or water vapor, from the outside, and can prevent deterioration of the characteristics of the photoelectric conversion. Therefore, it is possible to realize a dye-sensitized photoelectric conversion element module capable of maintaining long-term superior characteristics. In addition, since the dye-enhanced layer 3 and the counter electrode 5 are separated by the porous insulating layer 4, the dye-adhered semiconductor layer 3 of the dye-sensitized semiconductor layer 3 adheres to the pole 5, and the Z-shaped structure can be realized. The dye-sensitized photoelectric conversion element module of the dye-sensitized solar module has the same power generation performance as the embodiment of the dye-sensitized photoelectric conversion element module. The first embodiment is prepared on a glass having a size of 60 mm x 46 mm and a thickness of 4 mm. An amorphous solar FTO glass substrate (sheet resistance 10 Ω/ΕΙ) formed of a FTO film is formed, and the FTO is patterned by etching to form a crucible therebetween. A stripe pattern of 9 mm is formed in a width of 5 mm. Thereafter, acetone, an alcohol washing solution, and ultrapure water were sequentially used for ultrasonic cleaning, and sufficiently dried on one of the eight FTO films of the nine FTO films on the FTO glass substrate. The titanium oxide made of Solaronix has a stripe shape of 5 mm in width and 40 mm in length, and 8 strips (the total area of the electron-transmitting element mold is prevented from generating a special battery by using the durability semi-conductivity such as gas efficiency to explain the film for the glass substrate battery. Through the gap, the end of the alkali enamel is coated with '1 6cm2 -29 - 1380494 ) and coated by a screen printing machine. The coating is from the side of the glass plate, and the transparent Ti-Nanoxide TSP is sequentially coated. A Ti-Nanoxide DSP containing scattered particles was laminated to a thickness of 13/tzm to obtain a porous TiO 2 film having a total thickness of 20/im. The porous TiO 2 film was fired from an electric furnace at 500 ° C for 30 minutes, and then immersed in O. The lmol/L TiCl4 aqueous solution was kept at 70 ° C for 30 minutes, thoroughly washed with pure water and ethanol, dried, and then fired again at 500 ° C for 30 minutes in an electric furnace. In this way, a TiO 2 sintered body was produced. Next, screen printing using a commercially available TiO 2 particle (having a particle diameter of 200 nm), terpineol and ethyl cellulose was sized with a talc of 41 mm and a width of 5. A thickness of 5 mm and a thickness of 〇Am were applied to the above Ti〇2 sintered body. The butyl ruthenium 02 was smeared and dried, and the screen printing was made of Ti02, which was prepared by using commercially available carbon black and graphite particles, terpineol and ethyl cellulose as a counter electrode, and was 40 mm in length and 6 mm in width. A thickness of 30# m was applied to the above TiO 2 layer, and after being dried by coating, it was baked at 450 ° C for 30 minutes in an electric furnace. In this way, a porous insulating layer and a porous counter electrode are formed. Then, at 0. 5 mM cis bis(isocyanathio)-N,N-bis(2,2'-pyridine-4,4'-dicarboxylic acid) ruthenium (II) ditetrabutylammonium salt (N719 pigment) tert· The butanol/acetonitrile mixed solvent (volume ratio: 1:1) was immersed at room temperature for 48 hours, and the pigment was carried on the TiO 2 sintered body. The TiO 2 sintered body in which the dye was carried as described above was washed with acetonitrile and dried in a dark place. In this manner, a dye-sensitized TiO 2 sintered body was produced. 3 g of r-butyrolactone, dissolved sodium iodide (Nal) 0. 045g, 1·C • 30- 1380494 . Base-2,3-dimethylimidazolium iodide 1 lg, iodine (I2) 0·1 lg, 4·te-butylpyridine 0. 081 g, modulating the electrolyte composition. Then, the electrolyte composition thus prepared is applied to the surface on the counter electrode side using a dispenser, and is impregnated into the counter electrode, the porous insulating layer, and the dye-sensitized semiconductor layer, and the opposite pole. The excess electrolyte composition exuded from the porous insulating layer and the dye-sensitized semiconductor layer is cleanly wiped. β Next, a titanium foil having a size of 60 mm x 3 mm and a thickness of 30/zm was placed on the electrode-bonding portion provided on the transparent conductive layer formed of the FTO film at both ends of the FTO glass substrate by ultrasonic welding. Bonding, as the extraction electrode 6, 7» Next, on the bonding surface of the vapor-deposited aluminum gas barrier film, the protective film which bonds the hot-melt resin as an adhesive layer is cut into a size of 70 mm x 56 mm, and When the surface of the dye-sensitized photoelectric conversion element side was hot-pressed under reduced pressure, a dye-sensitized photoelectric conversion device was obtained. Then, the back surface of the glass substrate having a thickness of 4 mm formed as a dye-sensitized photoelectric conversion element module was sequentially ground by face honing and optical honing as a thickness of 0. 1 mm thin film glass substrate. Then, on the light incident side surface of the dye-sensitized photoelectric conversion element module, that is, the back surface of the thin film glass substrate, an AR film (trade name "ARCTOP") made of Asahi Glass cut into a size of 70 mm x 56 mm is attached, and the film is obtained from the thin film glass substrate. The exposed portion is bonded to the protective film adhered to the side of the dye-sensitized photoelectric conversion element by hot pressing, and the coated thin film glass substrate -31 - 1380494 is subjected to the above-mentioned work to obtain a desired dye-sensitized photoelectric conversion element. Module. The dye-sensitized photoelectric conversion element module is composed of eight dye-sensitized photoelectric conversion elements of a size of 5 mm x 40 mm connected in series. Example 2 used for thickness as a tempered glass treatment O. On a thin film glass substrate of 1 mm, a transparent conductive layer of ITO (thickness: 45 nm) / ΑΤΟ (thickness: 50 nm) similar to the FTO film of Example 1 was formed by sputtering, except that the back surface of the thin film glass substrate was not formed. A dye-sensitized photoelectric conversion element module was produced in the same manner as in Example 1 except for honing. (Comparative Example 1) The thickness of the glass substrate was maintained as 〇 unless the back surface honing of the glass substrate was not performed. A dye-sensitized photoelectric conversion element module was produced in the same manner as in Example 1 except for the case of 4 mm. (Comparative Example 2) An AR film was formed as a protective-thin S on the "back surface" of the thin film glass substrate, and the thickness was O. Lmm film glass substrate, coated with the same thickness O. A dye-sensitized photoelectric conversion element module was produced in the same manner as in Example 2 except that a protective film was not formed on the surface of the dye-sensitized photoelectric conversion element side. (Comparative Example 3) -32 - 1380494 . As a transparent conductive substrate, it is used on a polyethylene terephthalate (PEN) film, and a plastic film of an ITO film is vapor-deposited (sheet resistance 20 Ω / □, size 60 mm x 46 mm, thickness 0. 125mm), the ITO film is patterned by etching, and formed between 0. A stripe pattern of 9 mm width is formed. After that, acetone, alcohol, alkali-based cleaning solution, ultrapure water were used in sequence, and ultrasonic cleaning was performed to sufficiently dry it. One of the ends of the nine ITO films except the PEN/ITO substrate. On the ITO film of the ITO film, a titanium oxide paste was used as a titanium oxide paste for low-temperature film formation (manufactured by Peccell Technologies), and strips were formed in a stripe shape having a width of 5 mm and a length of 40 mm, and 8 strips (total area: 16 cm 2 ). The method is applied. After drying the film, it was kept on a hot plate at 150 ° C for 30 minutes. From this, the porous TiO 2 layer. Next, screen printing was carried out using TiO2 prepared by using commercially available TiO 2 particles (having a particle diameter of 200 nm), terpineol and ethyl cellulose, and having a length of 4 lmm and a width of 5. 5 mm and a thickness of 10 μm were applied to the above porous Ti02 layer. The TiO2 paste was dried, and the commercially available carbon black and the graphite particles 'terpineol and ethyl cellulose were used as the counter electrode to coat the screen printing with a length of 40 mm, a width of 6 mm, and a thickness of 30 μm. The cloth was coated on the above Ti 2 layer, and after being dried by coating, it was fired by an electric furnace at 4501 for 30 minutes. The TiO2 paste is dried, and the screen printing paste prepared by using carbon black and graphite particles 'factory alcohol and ethyl cellulose sold as a counter electrode is used, and has a length of 40 mm, a width of 6 mm, and a thickness of 30/. /m was applied to the above TiCh layer, and after being dried by slurrying, it was fired in an electric furnace at 15 ° C, -33 - 1380494 for 30 minutes. In this way, a porous insulating layer and a porous counter electrode are formed. Then, at 0. 5 mM cis bis(isocyanato)-indole, Ν-bis(2,2'-pyridine-4,4'-dicarboxylic acid) ruthenium (II) ditetrabutylammonium salt (Ν719 pigment) tert- The butanol/acetonitrile mixed solvent (volume ratio: 1:1) was immersed at room temperature for 48 hours to carry the dye on the porous TiO 2 layer. The porous TiO 2 layer carrying the dye was washed with acetonitrile and dried in the dark. In this way, a dye-sensitized porous TiO 2 layer was produced. 3 g of r-butyrolactone, dissolved sodium iodide (Nal) 0. 045g, 1-propyl-2,3-dimethylimidazolium iodide l. Llg, iodine (I2) O. Llg, 4-tert-butylpyridine 0. 081 g, modulating the electrolyte composition. Then, the electrolyte composition thus prepared is applied to the surface on the counter electrode side using a dispenser, and is impregnated into the counter electrode, the porous insulating layer, and the dye-sensitized semiconductor layer, and the opposite pole. The excess electrolyte composition exuded from the porous insulating layer and the dye-sensitized semiconductor layer is cleanly wiped. Next, the extraction electrode is placed on the transparent conductive layer formed by the end of the PEN"/ ITO g plate, and the size is 60 mm x 3 mm, and the thickness is 30//m, and the ultrasonic wave is passed through the ultrasonic wave. The welding method is joined to take out the electrode. Then, on the bonding surface of the vapor-deposited aluminum gas barrier film, the protective film which bonds the hot-melt resin as an adhesive layer is cut into a size of 70 mm×56 mm, and the surface of the dye-sensitized photoelectric conversion element is passed through the surface. When the hot pressing is performed under the pressure of -34 to 1380494, the surface of the dye-sensitized photoelectric conversion element module on the side of the dye-sensitized photoelectric conversion element is completely covered by the protective film. Through the above work, a target dye-sensitized photoelectric conversion element module is obtained. The dye-sensitized photoelectric conversion element module is composed of eight dye-sensitized photoelectric conversion elements of a size of 5 mm x 4 Omm connected in series. With respect to the dye-sensitized photoelectric conversion element modules of Examples 1 to 2 and Comparative Examples 1 to 3 prepared above, the photoelectric conversion efficiency under the irradiation conditions of AM 1 · 5 (1 s un ) was measured. Further, the dyeing of the dye-sensitized photoelectric conversion element module after the completion of the measurement was performed, and the radius of curvature before the occurrence of the fracture was calculated. The results are shown in Table 1. [Table 1] Photoelectric conversion efficiency % Minimum radius of curvature (mm) _ weight (g) Example 1 6. 71 7. 3 1. 69 Example 2 6. 55 5. 9 1. 72 Example 3 6. 65 7. 5 1. 20 Comparative Example 1 6. 80 cannot be measured without bending. 6 Comparative Example 2 6. 66 23. 1 1. 45 Comparative Example 3 1. 29 3. 1 (production of film peeling) 50 Comparative Example 4 6. 51 9. 8 1. 14 * Data is the average 制作 prepared by the number of samples 5. From Table 1, the dye-sensitized photoelectric conversion element modules of Examples 1 and 2 are known, and the photoelectric conversion efficiency is excellent, and the minimum radius of curvature is small and light weight is %. In Comparative Example 1, the thickness of the glass substrate was 4 mm, and the photoelectric conversion efficiency was high. However, the dye-sensitized photoelectric conversion element module was not bent, and the radius of curvature was not measured, and the weight was extremely heavy. In Comparative Example 2, the photoelectric conversion efficiency was high, but in comparison with Examples 1 and 2, the radius of curvature was extremely large. In Comparative Example 3, a thin-film glass substrate was not used, and a PEN/ITO substrate was used to prepare a dye-sensitized photoelectric conversion element module. When the porous TiO 2 layer was formed, it did not pass through 500 ° C. Due to the firing process, the photoelectric conversion efficiency is extremely low. Next, a dye-sensitized photoelectric conversion element module according to a second embodiment of the present invention will be described. As shown in FIG. 6, in the dye-sensitized photoelectric conversion element module, a protective film 11 is adhered to the back surface of the thin film glass substrate 1, and a protective film 9 adhered to the surface of the dye-sensitized photoelectric conversion element is attached. The film is folded back on the end surface of the film φ glass substrate 1 and bonded to the back surface of the film glass substrate 1. The other configuration of the color-sensitized photoelectric conversion element module is the same as that of the dye-sensitized photoelectric conversion element module according to the first embodiment. The method for manufacturing the dye-sensitized photoelectric conversion element module is that the protective film 9 is folded back on the end surface of the film glass substrate 1 except that the protective film 11 is not adhered to the back surface of the film glass substrate 1, and The method for manufacturing the dye-sensitized photoelectric conversion element module of the first embodiment is the same. According to the second embodiment, the same as that of the first embodiment can be obtained. The embodiment of the dye-sensitized photoelectric conversion element module will be described. In the third embodiment, the AR film is not adhered to the back surface of the film glass substrate, and the protective film adhered to the surface of the dye-sensitized photoelectric conversion element is folded back. A dye-sensitized photoelectric conversion element module was produced in the same manner as in Example 1 except that the end surface of the film-36-1380494 glass substrate was bonded to the back surface of the film glass substrate. (Comparative Example 4) The size of the protective film adhered to the surface of the dye-sensitized photoelectric conversion element was φ 58 mm x 44 mm which is smaller than the film glass substrate size (60 mm x 46 mm) - and the end face of the film glass substrate was exposed and adhered A dye-sensitized photoelectric conversion element module was produced in the same manner as in Example 3 except that the protective film was used. With respect to the dye-sensitized photoelectric conversion element modules of Example 3 and Comparative Example 4 produced as above, the photoelectric conversion efficiency under the irradiation conditions of AM 1 · 5 (1 sun) was measured. Further, a bending test of the dye-sensitized photoelectric conversion element module after the measurement was completed was performed, and the radius of curvature before the occurrence of the fracture was calculated. The results are shown in Table 1. • The dye-sensitized photoelectric conversion element module of the third embodiment is known from Table 1, and has excellent photoelectric conversion efficiency, a small minimum radius of curvature, and a light weight. In Comparative Example 4, the photoelectric conversion efficiency was high, the size of the protective film was smaller than that of the thin film glass substrate, and the end surface of the thin film glass substrate was not covered by the protective film. Compared with Example 3, the radius of curvature was large. Next, a dye-sensitized photoelectric conversion element module according to a third embodiment of the present invention will be described. As shown in FIG. 7, for the dye-sensitized photoelectric conversion element module, the counter electrode 5 is selected from the group consisting of Ti, Ni, Cr, Fe, Nb, Ta, W, Co& -37- 1380494
Zr所成的群之至少1種類以上元素的金屬或合金所成的 箔之多孔質絕緣層4側的單面，設置包含選自Pt、Ru、ΙΓ 及C所成的群之至少1種類以上元素之觸媒層的構成，或 包含選自Pt、Ru、Ir及C所成的群之至少1種類以上元 素之材料所成的箔而成。並且，1個之色素增感型光電變 換元件的對極5之一端係藉由導電材料12，與鄰接之色 素增感型光電變換元件之透明導電層2加以接合。其色素 增感光電變換元件模組之其他的構成係與根據第1實施型 態之色素增感光電變換元件模組同樣。 接著，對於其色素增感光電變換元件模組之製造方法 加以說明。 首先，與第1實施型態同樣地進行工程，形成至多孔 質絕緣層4之後，於各透明導電層2上之對極5的接合部 ，形成導電材料12，於特定形狀之金屬或合金所成的箔 之單面，形成具有觸媒層，或具有催化活性之材料所成的 箔而成之對極5，與其導電材料12接合。 接著，由與第1實施形態同樣作爲，形成取出電極6 ，Ί。 " … " —— 接著，除了對各色素增感光電變換元件預先形成注液 口之部分，於各色素增感光電變換元件之間的對極5與多 孔質絕緣層4之間的部份及對極5的全面，形成黏接層8 〇 接著’從對各色素增感光電變換元件預先形成注液口 ’將電解液注液，至少對於色素增感半導體層3及多孔質 1380494 絕緣層4之全體，典型而言，浸含電解質於此等色素增感 半導體層3及多孔質絕緣層4與對極5之全體。 之後’與第1實施形態同樣地進行保護薄膜9之黏接 以後的工程’製造色素增感光電變換元件模組。 如根據其第3實施形態，加上於與第1實施形態相同 的優點’可得到如以下的優點。即，經由對極5係於金屬 或合金所成的箔之上方，具有觸媒層者，或具有催化活性 之材料所成的箔而成之故而可薄化構成對極5者，可薄型 化及輕量化色素增感光電變換元件模組。另外，構成對極 5之金屬或合金所成的箔及觸媒層之材料或具有催化活性 之材料係選擇幅度廣，無在對極的材料面之限制。更且， 色素增感半導體層3與對極5係由多孔質絕緣層4所間隔 之故，可防止色素增感半導體層3的色素附著對極5者， 從不會產生特性的劣化，可實現具有與Z型構造之色素增 感太陽能電池模組同等之發電性能的色素增感光電變換元 件模組。 對於其色素增感光電變換元件模組之實施例加以說明 實施例4 使用FTO玻璃基板，與實施例1同樣地進行工程， 製作色素增感Ti02燒結體之後，將向異性導電塗漿，以 〇.5mm寬度，於條紋狀的色素增感Ti02燒結體，呈成爲 平行地加以塗部而使其乾燥。 -39- 1380494 接著，於厚度0.05mm之駄箱的單面，將0.05mM之 氯化白金酸的異丙醇（IPA)溶液進行噴塗，將以3 85 °C 燒成之對極切割成6mm><4〇mm的尺寸，將噴塗氯化白金 酸的面，朝向色素增感Ti02燒結體側，進行位置配合之 後，經由熱壓著接合上述之向異性導電塗漿。 於FTO玻璃基板上，殘留住液用之直徑1mm的圖案 ，呈完全被覆各色素增感光電變換元件地，以網版印刷而 塗佈UV硬化型黏接劑。塗佈後，氣泡完全消失後，以輸 送帶式之UV曝光機，於UV硬化型黏接劑照射紫外光而 使其硬化。 接著，與實施例1同樣地，將調製之電解質組成物， 如上述從所準備之直徑1mm之注液口，在減壓下進行注 入後，在0.4MPa之加壓下進行30分鐘保持，使電解液完 全地浸透於各色素增感光電變換元件內。由如此，於色素 增感Ti〇2燒結體及多孔質絕緣層，浸含電解質。 接著，將上述之電解液的注液口，經由UV硬化型黏 接劑進行密封之後，由與實施例1同樣作爲，於色素增感 光電變換元件_側黏接保護薄膜之同時，硏磨玻璃基板，作 爲厚度0.1mm之薄膜玻璃基板之後，於其薄膜玻璃基板 的背面，黏接保護薄膜，在從薄膜玻璃基板露出之部分， 接合此等保護薄膜，得到色素增感光電變換元件模組。接 著，對於根據本發明之第4實施型態的色素增感光電變換 元件模組加以說明。 對於此色素增感光電變換元件模組，在根據第1實施 -40- 1380494 型態之色素增感光電變換元件模組，電解質乃包含碘，且 包含至少具有1個異氰酸酯基（-NCO )之化合物，最佳 係更且，其化合物乃於相同分子內，除異氰酸酯基以外至 少含有1個含氮官能基，或除其化合物以外，更包含至少 具有1個以上含氮官能基之化合物的電解質組成物所成。 對於至少具有1個以上異氰酸酯基（-NCO )之化合物， 並無特別加以限定，但與電解質的溶劑或電解質鹽，其他 的添加劑相溶者爲佳。至少具有1個以上含氮官能基之化 合物係最佳爲胺系化合物，但並不限定於此。對於胺系化 合物，並無特別加以限定，但與電解質的溶劑或電解質鹽 ，其他的添加劑相溶者爲佳。對於如此至少具有1個以上 異氰酸酯基之化合物，使含氮官能基共存時，特別對於色 素增感光電變換元件模組之開放電壓的增加有大的貢獻。 至少具有1個以上異氰酸酯基之化合物係具體而言，例如 異氰酸苯基，異氰酸2-氯乙基，異氰酸m-氯苯胂，異氰 酸環己基，異氰酸〇-甲苯基，異氰酸P-甲苯基，異氰酸 η-己基，2,4-二異氰酸甲代苯撑，二異氰酸環己烷’ 4,4’-二異氰酸亞甲基二苯基等，但並不限定於此。另外’胺系 化合物係具體而言，例如有4-特-丁基吡啶、苯胺、Ν，Ν-二甲基苯胺、Ν -甲基苯并咪唑等，但並不限定於此。 上述以外的構成係與根據第1實施型態之色素增感光 電變換元件模組同樣。 如根據第4實施型態，加上於與第1實施型態同樣的 優點，電解質乃經由包含至少具有1個以上異氰酸酯基之 -41 - 1380494 化合物的電解質組成物所成者，可使短路電流及開放電壓 的雙方增加，由此可得到光電變換效率極高，高色素增感 光電變換元件模組之優點。對於其色素增感光電變換元件 模組之實施例加以說明。 實施例5 在實施例1，於調製電解質組成物時，於r-丁内酯 3g，加上於碘化鈉（NaI)0·045g、l-丙基-2,3-二甲基咪 唑碘化物l.llg、碘（h) O.llg' 4 -特-丁基吡啶〇.〇81g， 溶解異氰酸苯基〇.〇71g(〇.2mol/L)。其他與實施例1 同樣，得到色素增感光電變換元件模組。 以上，對於本發明之實施型態及實施例做了具體說明 ’但本發明非限定於上述之實施型態及實施例，依據本發 明之技術性思想，可進行各種之變形。 例如’在上述之實施型態及實施例所舉出之數値，構 造，形狀，材料’原料’處理等不過爲例子，而亦可因應 必要而使用與此等相異之數値，構造，形狀，材料，原料 ，處理等。 — 【圖式簡單說明】 〔圖1〕圖1乃顯示根據本發明之第i實施形態之色 素增感型光電變換元件模組之剖面圖。 〔圖2〕圖2乃顯示根據本發明之第1實施形態之色 素增感型光電變換元件模組之要部的擴大剖面圖。 -42- 1380494 〔圖3〕圖3乃顯示根據本發明之第1實施形態之色 素增感型光電變換元件模組之平面圖。 〔圖4〕圖4乃顯示根據本發明之第1實施形態之色 素增感型光電變換元件模組之要部的擴大平面圖。 〔圖5〕圖5乃爲了說明根據本發明之第1實施形態 之色素增感型光電變換元件模組之製造方法的剖面圖。 〔圖6〕圖6乃顯示根據本發明之第2實施形態之色 • 素增感型光電變換元件模組之剖面圖。 〔圖7〕圖7乃顯示根據本發明之第3實施形態之色 素增感型光電變換元件模組之要部的擴大剖面圖。 【主要元件符號說明】 1 :薄膜坡璃基板 2 :透明導電層 3:色素增感半導體層 # 4 :多孔質絕緣層 5 :對極 6 :取出電極 8 :黏接層 9 :保護薄膜 1〇 :黏接層 11 :保護薄膜 -43-At least one type of a group selected from the group consisting of Pt, Ru, ΙΓ, and C is formed on one side of the porous insulating layer 4 side of the foil formed of a metal or an alloy of at least one type of elements of the group formed by Zr. The composition of the catalyst layer of the element or a foil made of a material selected from at least one type of elements selected from the group consisting of Pt, Ru, Ir, and C. Further, one end of the counter electrode 5 of one dye-sensitized photoelectric conversion element is bonded to the transparent conductive layer 2 of the adjacent color sensitization photoelectric conversion element by the conductive material 12. The other configuration of the dye-sensitized photoelectric conversion element module is the same as that of the dye-sensitized photoelectric conversion element module according to the first embodiment. Next, a method of manufacturing the dye-sensitized photoelectric conversion element module will be described. First, in the same manner as in the first embodiment, after the porous insulating layer 4 is formed, the conductive material 12 is formed on the joint portion of the counter electrode 5 on each of the transparent conductive layers 2, and the metal or alloy of a specific shape is formed. The single side of the formed foil forms a counter electrode 5 formed of a foil having a catalyst layer or a catalytically active material, and is bonded to the conductive material 12. Next, in the same manner as in the first embodiment, the extraction electrode 6 is formed. " ... " - Next, the portion between the counter electrode 5 and the porous insulating layer 4 between the respective dye-sensitized photoelectric conversion elements, except for the portion where the liquid-filling port is formed in advance for each dye-sensitized photoelectric conversion element The adhesive layer 8 is formed in the entirety of the portion and the counter electrode 5, and then the electrolyte solution is injected from the dye inlet port for each dye-sensitized photoelectric conversion element, and at least the dye-sensitized semiconductor layer 3 and the porous 1380494 are insulated. The entire layer 4 is typically impregnated with the dye-sensitized semiconductor layer 3, the porous insulating layer 4, and the counter electrode 5 as a whole. Then, in the same manner as in the first embodiment, the process of bonding the protective film 9 is carried out to manufacture a dye-sensitized photoelectric conversion element module. According to the third embodiment, the same advantages as those of the first embodiment are added, and the following advantages can be obtained. In other words, the counter electrode 5 is formed by a catalyst layer or a foil made of a catalytically active material, and the thinner layer 5 can be made thinner. And a lightweight pigment-sensitized photoelectric conversion element module. Further, the material of the foil or the catalyst layer formed of the metal or alloy of the pole 5 or the material having catalytic activity is widely selected, and there is no limitation on the material surface of the counter electrode. Further, since the dye-sensitized semiconductor layer 3 and the counter electrode 5 are separated by the porous insulating layer 4, it is possible to prevent the dye adhesion of the dye-sensitized semiconductor layer 3 to the pole 5, and deterioration of characteristics is not caused. A dye-sensitized photoelectric conversion element module having the same power generation performance as the dye-sensitized solar cell module of the Z-type structure is realized. Example of the example of the dye-sensitized photoelectric conversion element module. Example 4 Using the FTO glass substrate, the dye-sensitized TiO 2 sintered body was produced in the same manner as in Example 1, and then the conductive paste was applied to the opposite side. The stripe-shaped dye-sensitized TiO 2 sintered body has a width of 5 mm and is applied in parallel to be dried. -39- 1380494 Next, a 0.05 mM solution of chlorophosphoric acid in isopropyl alcohol (IPA) was sprayed on one side of a 0.05 mm thick box, and the counter electrode was fired at 3 85 ° C to cut into 6 mm. <4〇mm size, the surface of the chlorotin acid-coated surface is applied to the dye-sensitized TiO2 sintered body side, and after the position is matched, the above-described anisotropic conductive paste is bonded by hot pressing. On the FTO glass substrate, a pattern having a diameter of 1 mm for liquid remains, and each of the dye-sensitized photoelectric conversion elements was completely coated, and a UV-curable adhesive was applied by screen printing. After the application, the bubbles completely disappeared, and the UV-curable adhesive was irradiated with ultraviolet light to be hardened by a UV-type exposure machine. Then, in the same manner as in Example 1, the prepared electrolyte composition was injected under reduced pressure from the prepared liquid injection port having a diameter of 1 mm, and then held under a pressure of 0.4 MPa for 30 minutes. The electrolyte was completely impregnated into each of the dye-sensitized photoelectric conversion elements. Thus, the dye-sensitized Ti〇2 sintered body and the porous insulating layer are impregnated with an electrolyte. Then, after the liquid injection port of the above-mentioned electrolytic solution was sealed with a UV-curable adhesive, the same manner as in Example 1 was carried out, and the dye-sensitized photoelectric conversion element-side adhesive film was bonded while honing the glass. After the substrate was used as a film glass substrate having a thickness of 0.1 mm, a protective film was adhered to the back surface of the film glass substrate, and the protective film was bonded to a portion exposed from the film glass substrate to obtain a dye-sensitized photoelectric conversion element module. Next, a dye-sensitized photoelectric conversion element module according to a fourth embodiment of the present invention will be described. In the dye-sensitized photoelectric conversion element module according to the first aspect of the invention, the electrolyte-containing photoelectric conversion element module contains iodine and contains at least one isocyanate group (-NCO). Further, the compound is preferably an electrolyte containing at least one nitrogen-containing functional group in addition to the isocyanate group, or a compound having at least one nitrogen-containing functional group in addition to the compound in the same molecule. The composition is made. The compound having at least one or more isocyanate groups (-NCO) is not particularly limited, but is preferably compatible with a solvent or an electrolyte salt of an electrolyte and other additives. The compound having at least one nitrogen-containing functional group is preferably an amine-based compound, but is not limited thereto. The amine compound is not particularly limited, but it is preferably a solvent or an electrolyte salt of an electrolyte or other additives. When the nitrogen-containing functional group coexists in the compound having at least one or more isocyanate groups, the increase in the open voltage of the color-sensitized photoelectric conversion element module is greatly contributed. Compounds having at least one isocyanate group are specifically, for example, phenyl isocyanate, 2-chloroethyl isocyanate, m-chlorophenylhydrazine isocyanate, cyclohexyl isocyanate, guanidinium isocyanate- Tolyl, isocyanate P-tolyl, isocyanate η-hexyl, 2,4-diisocyanate phenylene, diisocyanate cyclohexane '4,4'-diisocyanate Diphenyl or the like, but is not limited thereto. Further, the 'amine-based compound is specifically, for example, 4-tert-butylpyridine, aniline, anthracene, fluorene-dimethylaniline or decyl-methylbenzimidazole, but is not limited thereto. The configuration other than the above is the same as that of the dye-sensitized photoelectric conversion element module according to the first embodiment. According to the fourth embodiment, in addition to the same advantages as in the first embodiment, the electrolyte can be made to have a short-circuit current via an electrolyte composition containing a compound of -41 - 1380494 having at least one isocyanate group. Both the open voltage and the open voltage are increased, whereby the photoelectric conversion efficiency is extremely high, and the high dye-sensitized photoelectric conversion element module is advantageous. An embodiment of the dye-sensitized photoelectric conversion element module will be described. Example 5 In Example 1, when preparing the electrolyte composition, 3 g of r-butyrolactone was added to sodium iodide (NaI) 0.045 g, and 1-propyl-2,3-dimethylimidazolium iodide was added. Compound l.llg, iodine (h) O.llg' 4 -tert-butylpyridinium 〇 81g, dissolved phenyl hydrazine isocyanate. 〇 71g (〇. 2mol / L). In the same manner as in Example 1, a dye-sensitized photoelectric conversion element module was obtained. The embodiments and the embodiments of the present invention have been described in detail above. However, the present invention is not limited to the above-described embodiments and examples, and various modifications can be made in accordance with the technical idea of the present invention. For example, the number, structure, shape, and material 'raw material' treatment of the above-described embodiments and examples are merely examples, and the same may be used as necessary. Shape, material, raw materials, processing, etc. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing a color sensitization type photoelectric conversion element module according to an i-th embodiment of the present invention. [ Fig. 2] Fig. 2 is an enlarged cross-sectional view showing a main part of a color sensitization photoelectric conversion element module according to a first embodiment of the present invention. [Fig. 3] Fig. 3 is a plan view showing a color sensitization type photoelectric conversion element module according to the first embodiment of the present invention. [Fig. 4] Fig. 4 is an enlarged plan view showing a main part of a color sensitization photoelectric conversion element module according to the first embodiment of the present invention. [ Fig. 5] Fig. 5 is a cross-sectional view showing a method of manufacturing a dye-sensitized photoelectric conversion element module according to a first embodiment of the present invention. Fig. 6 is a cross-sectional view showing a color sensitized photoelectric conversion element module according to a second embodiment of the present invention. [ Fig. 7] Fig. 7 is an enlarged cross-sectional view showing a main part of a color sensitization photoelectric conversion element module according to a third embodiment of the present invention. [Description of main component symbols] 1 : Film glass substrate 2 : Transparent conductive layer 3 : Pigment-sensitized semiconductor layer # 4 : Porous insulating layer 5 : Counter electrode 6 : Take-out electrode 8 : Adhesive layer 9 : Protective film 1〇 : adhesive layer 11 : protective film -43-